In Situ Measurement of Evolving Excited-State Dynamics During Deposition and Processing of Organic Films by Single-Shot Transient Absorption.

A significant advantage of organic semiconductors over many of their inorganic counterparts is solution processability. However, solution processing commonly yields heterogeneous films with properties that are highly sensitive to the conditions and parameters of casting and processing. Measuring the key properties of these materials in situ, during film production, can provide new insight into the mechanism of these processing steps and how they lead to the emergence of the final organic film properties. The excited-state dynamics is often of import in photovoltaic, electronic, and light-emitting devices. This review focuses on single-shot transient absorption, which measures a transient spectrum in a single shot, enabling the rapid measurement of unstable chemical systems such as organic films during their casting and processing. We review the principles of instrument design and provide examples of the utility of this spectroscopy for measuring organic films during their production.

An operando spectroscopic investigation of the Re2O7.2H2O adduct obtained by controlled hydration of Re2O7.

We provide here a comprehensive investigation spectroscopic of the controlled hydration of Re2O7 using Raman, FTIR and XAS techniques in complement with ab initio modelling for confirming the spectral assignments. Hence, the Raman signature of Re2O7.2H2O was obtained, and the evolution kinetics was investigated to provide a detailed description of the hydration process.

Ligand Hydrogenation during Hydroformylation Catalysis Detected by In Situ High-Pressure Infra-Red Spectroscopic Analysis of a Rhodium/Phospholene-Phosphite Catalyst.

Phospholane-phosphites are known to show highly unusual selectivity towards branched aldehydes in the hydroformylation of terminal alkenes. This paper describes the synthesis of hitherto unknown unsaturated phospholene borane precursors and their conversion to the corresponding phospholene-phosphites. The relative stereochemistry of one of these ligands and its Pd complex was assigned with the aid of X-ray crystal structure determinations. These ligands were able to approach the level of selectivity observed for phospholane-phosphites in the rhodium-catalysed hydroformylation of propene. High-pressure infra-red (HPIR) spectroscopic monitoring of the catalyst formation revealed that whilst the catalysts showed good thermal stability with respect to fragmentation, the C=C bond in the phospholene moiety was slowly hydrogenated in the presence of rhodium and syngas. The ability of this spectroscopic tool to detect even subtle changes in structure, remotely from the carbonyl ligands, underlines the usefulness of HPIR spectroscopy in hydroformylation catalyst development.

Harnessing Nuclear Magnetic Resonance Spectroscopy to Decipher Structure and Dynamics of Clathrate Hydrates in Confinement: A Perspective.

This perspective outlines recent developments in the field of NMR spectroscopy, enabling new opportunities for in situ studies on bulk and confined clathrate hydrates. These hydrates are crystalline ice-like materials, built up from hydrogen-bonded water molecules, forming cages occluding non-polar gaseous guest molecules, including CH4, CO2 and even H2 and He gas. In nature, they are found in low-temperature and high-pressure conditions. Synthetic confined versions hold immense potential for energy storage and transportation, as well as for carbon capture and storage. Using previous studies, this report highlights static and magic angle spinning NMR hardware and strategies enabling the study of clathrate hydrate formation in situ, in bulk and in nano-confinement. The information obtained from such studies includes phase identification, dynamics, gas exchange processes, mechanistic studies and the molecular-level elucidation of the interactions between water, guest molecules and confining interfaces.

The Coking of a Solid Catalyst Rationalized with Combined Raman and Fluorescence Lifetime Microscopy.

The formation of carbon deposits is a major deactivation pathway for solid catalysts. Studying coking on industrially relevant catalysts is, however, often challenging due to the sample heterogeneity. That is especially true for zeolite-containing catalysts where fluorescence often hampers their characterization with Raman spectroscopy. We turned this disadvantage into an advantage and combined Raman and fluorescence (lifetime) microscopy to study the coking behavior of an equilibrium catalyst material used for fluid catalytic cracking of hydrocarbons. The results presented illustrate that this approach can yield new insights in the physicochemical processes occurring within zeolite-containing catalyst particles during their coking process. Ex situ analyses of single catalyst particles revealed considerable intra-sample heterogeneities. The sample-averaged Raman spectra showed a higher degree of graphitization when the sample was exposed to more hexane, while the sample-averaged fluorescence lifetime showed no significant trend. Simultaneous in situ Raman and fluorescence (lifetime) microscopy, used to follow the coking and the regeneration of single particles, gave more insights in the changing fluorescence dynamics. During the coking, the rise and decline of the average fluorescence lifetime suggested the prolonged presence of smaller coke species that are quenched more and more by adjacent larger polyaromatics acting as Förster-resonance-energy-transfer acceptors.

Polyelectrolyte Additive-Modulated Interfacial Microenvironment Boosting CO2 Electrolysis in Acid.

Acidic CO2 electrolysis offers a promising strategy to achieve high carbon utilization and high energy efficiency. However, challenges remain in suppressing the competitive hydrogen evolution reaction (HER) and improving product selectivity. High concentrations of potassium ions (K+) can suppress HER and accelerate CO2 reduction, but they still inevitably suffer from salt precipitation problems. In this study, we demonstrate that the sulfonate-based polyelectrolyte, polystyrene sulfonate (PSS), enables to reconstruct the electrode-electrolyte interface to significantly enhance the acidic CO2 electrolysis. Mechanistic studies reveal that PSS induces high local K+ concentrations through electrostatic interaction between PSS anions and K+. In situ spectroscopy reveals that PSS reshapes the interfacial hydrogen-bond (H-bond) network, which is attributed to the H-bonds between PSS anions and hydrated proton as well as the steric hindrance of the additive molecules. This greatly weakens proton transfer kinetics and leads to the suppression of undesirable HER. As a result, a Faradaic efficiency of 93.9% for CO can be achieved at 250 mA cm-2, simultaneous with a high single-pass carbon efficiency of 72.2% on commercial Ag catalysts in acid. This study highlights the important role of the electrode-electrolyte interface induced by polyelectrolyte additives in promoting electrocatalytic reactions.

Unveiling the Aggregation of M-N-C Single-Atom Electrocatalysts into Highly Efficient MOOH Nanoclusters during Alkaline Water Oxidation.

M-N-C-type single-atom catalysts (SACs) are highly efficient for the electrocatalytic oxygen evolution reaction (OER). And the isolated metal atoms are usually considered real active sites. However, the oxidative structural evolution of coordinated N during the OER will probably damage the structure of M-N-C, hence resulting in a completely different reaction mechanism. Here, we reveal the aggregation of M-N-C materials during the alkaline OER. Taking Ni-N-C as an example, multiple characterizations show that the coordinated N on the surface of Ni-N-C is almost completely dissolved in the form of NO3-, accompanied by the generation of abundant O functional groups on the surface of the carbon support. Accordingly, the Ni-N bonds are broken. Through a dissolution-redeposition mechanism and further oxidation, the isolated Ni atoms are finally converted to NiOOH nanoclusters supported by carbon as the real active sites for the enhanced OER. Fe-N-C and Co-N-C also have similar aggregation mechanism. Our findings provide unique insight into the structural evolution and activity origin of M-N-C-based catalysts under electrooxidative conditions.

Deciphering the Mechanism of Crystallization of UiO-66 Metal-Organic Framework.

Zirconium-containing metal-organic framework (MOF) with UiO-66 topology is an extremely versatile material, which finds applications beyond gas separation and catalysis. However, after more than 10 years after the first reports introducing this MOF, understanding of the molecular-level mechanism of its nucleation and growth is still lacking. By means of in situ time-resolved high-resolution mass spectrometry, Zr K-edge X-ray absorption spectroscopy, magic-angle spinning nuclear magnetic resonance spectroscopy, and X-ray diffraction it is showed that the nucleation of UiO-66 occurs via a solution-mediated hydrolysis of zirconium chloroterephthalates, whose formation appears to be autocatalytic. Zirconium-oxo nodes form directly and rapidly during the synthesis, the formation of pre-formed clusters and stable non-stoichiometric intermediates are not observed. The nuclei of UiO-66 possess identical to the crystals local environment, however, they lack long-range order, which is gained during the crystallization. Crystal growth is the rate-determining step, while fast nucleation controls the formation of the small crystals of UiO-66 with a narrow size distribution of about 200 nanometers.

Dimensionality Mediated Highly Repeatable and Fast Transformation of Coordination Polymer Single Crystals for All-Optical Data Processing.

A family of coordination polymers (CPs) based on dynamic structural elements are of great fundamental and commercial interest addressing modern problems in controlled molecular separation, catalysis, and even data processing. Herein, the endurance and fast structural dynamics of such materials at ambient conditions are still a fundamental challenge. Here, we report on the design of a series of Cu-based CPs [Cu(bImB)Cl2] and [Cu(bImB)2Cl2] with flexible ligand bImB (1,4-bis(imidazol-1-yl)butane) packed into one- and two-dimensional (1D, 2D) structures demonstrating dimensionality mediated flexibility and reversible structural transformations. Using the laser pulses as a fast source of activation energy, we initiate CP heating followed by anisotropic thermal expansion and 0.2-0.8% volume changes with the record transformation rates from 2220 to 1640 s-1 for 1D and 2D CPs, respectively. The endurance over 103 cycles of structural transformations, achieved for the CPs at ambient conditions, allows demonstrating optical fiber integrated all-optical data processing.

Size-Dependent Dispersion of Rhodium Clusters into Isolated Single Atoms at Low Temperature and the Consequences for CO Oxidation Activity.

Understanding the dynamic structural evolution of supported metal clusters under reaction conditions is crucial to develop structure reactivity relations. Here, we followed the structure of different size Rh clusters supported on Al2 O3 using in situ/operando spectroscopy and ex situ aberration-corrected electron microscopy. We report a dynamic evolution of rhodium clusters into thermally stable isolated single atoms upon exposure to oxygen and during CO oxidation. Rh clusters partially disperse into single atoms at room temperature and the extent of dispersion increases as the Rh size decreases and as the reaction temperature increases. A strong correlation is found between the extent of dispersion and the CO oxidation kinetics. More importantly, dispersing Rh clusters into single atoms increases the activity at room temperature by more than two orders of magnitude due to the much lower activation energy on single atoms (40 vs. 130 kJ/mol). This work demonstrates that the structure and reactivity of small Rh clusters are very sensitive to the reaction environment.

Polarization-Dependent Sum-Frequency-Generation Spectroscopy for In Situ Tracking of Nanoparticle Morphology.

The surface structure of oxide-supported metal nanoparticles can be determined via characteristic vibrations of adsorbed probe molecules such as CO. Usually, spectroscopic studies focus on peak position and intensity, which are related to binding geometries and number of adsorption sites, respectively. Employing two differently prepared model catalysts, it is demonstrated that polarization-dependent sum-frequency-generation (SFG) spectroscopy reveals the average surface structure and shape of the nanoparticles. SFG results for different particle sizes and morphologies are compared to direct real-space structure analysis by TEM and STM. The described feature of SFG could be used to monitor particle restructuring in situ and may be a valuable tool for operando catalysis.

Comparing the effect of different sample conditions and spectral libraries on the prediction accuracy of soil properties from near- and mid-infrared spectra at the field-scale.

The prediction accuracy of soil properties by proximal soil sensing has made their application more practical. However, in order to gain sufficient accuracy, samples are typically air-dried and milled before spectral measurements are made. Calibration of the spectra is usually achieved by making wet chemistry measurements on a subset of the field samples and local regression models fitted to aid subsequent prediction. Both sample handling and wet chemistry can be labour and resource intensive. This study aims to quantify the uncertainty associated with soil property estimates from different methods to reduce effort of field-scale calibrations of soil spectra. We consider two approaches to reduce these expenses for predictions made from visible-near-infrared ((V)NIR), mid-infrared (MIR) spectra and their combination. First, we considered reducing the level of processing of the samples by comparing the effect of different sample conditions (in-situ, unprocessed, air-dried and milled). Second, we explored the use of existing spectral libraries to inform calibrations (based on milled samples from the UK National Soil Inventory) with and without 'spiking' the spectral libraries with a small subset of samples from the study fields. Prediction accuracy of soil organic carbon, pH, clay, available P and K for each of these approaches was evaluated on samples from agricultural fields in the UK. Available P and K could only be moderately predicted with the field-scale dataset where samples were milled. Therefore this study found no evidence to suggest that there is scope to reduce costs associated with sample processing or field-scale calibration for available P and K. However, the results showed that there is potential to reduce time and cost implications of using (V)NIR and MIR spectra to predict soil organic carbon, clay and pH. Compared to field-scale calibrations from milled samples, we found that reduced sample processing lowered the ratio of performance to inter-quartile range (RPIQ) between 0% and 76%. The use of spectral libraries reduced the RPIQ of predictions relative to field-scale calibrations from milled samples between 54% and 82% and the RPIQ was reduced between 29% and 70% for predictions when spectral libraries were spiked. The increase in uncertainty was specific to the combination of soil property and sensor analysed. We conclude that there is always a trade-off between prediction accuracy and the costs associated with soil sampling, sample processing and wet chemical analysis. Therefore the relative merits of each approach will depend on the specific case in question.

Facet-specific Active Surface Regulation of Bix MOy (M=Mo, V, W) Nanosheets for Boosted Photocatalytic CO2 reduction.

Photocatalytic performance can be optimized via introduction of reactive sites. However, it is practically difficult to engineer these on specific photocatalyst surfaces, because of limited understanding of atomic-level structure-activity. Here we report a facile sonication-assisted chemical reduction for specific facets regulation via oxygen deprivation on Bi-based photocatalysts. The modified Bi2 MoO6 nanosheets exhibit 61.5 and 12.4 µmol g-1 for CO and CH4 production respectively, ≈3 times greater than for pristine catalyst, together with excellent stability/reproducibility of ≈20 h. By combining advanced characterizations and simulation, we confirm the reaction mechanism on surface-regulated photocatalysts, namely, induced defects on highly-active surface accelerate charge separation/transfer and lower the energy barrier for surface CO2 adsorption/activation/reduction. Promisingly, this method appears generalizable to a wider range of materials.

Probing Molybdenum Active Sites during In Situ Photoreduction of the Mo6+/SiO2 Catalyst.

The photoreduction of the Mo6+/SiO2 system with CO was investigated in situ, employing a recently developed experimental setup allowing for the acquisition of transmission FT-IR spectra under simultaneous UV irradiation. Carbon monoxide, besides acting as a reducing agent in such processes, is also a useful probe molecule able to detect coordinatively unsaturated sites exposed on the surface. The unprecedented quality of the spectroscopic data, obtained as a function of the reduction time, allowed us to better rationalize the different mechanisms previously proposed for the photoreduction process. These results, coupled with UV-Vis spectroscopic data, shed light on the oxidation state and surface structure of supported molybdenum species, which are key active sites for several important reactions, such as selective oxidation, polymerization, hydrodesulfurization, epoxidation and olefin metathesis.

Reaction Mechanism of Pd-Catalyzed "CO-Free" Carbonylation Reaction Uncovered by In Situ Spectroscopy: The Formyl Mechanism.

"CO-free" carbonylation reactions, where synthesis gas (CO/H2 ) is substituted by C1 surrogate molecules like formaldehyde or formic acid, have received widespread attention in homogeneous catalysis lately. Although a broad range of organics is available via this method, still relatively little is known about the precise reaction mechanism. In this work, we used in situ nuclear magnetic resonance (NMR) spectroscopy to unravel the mechanism of the alkoxycarbonylation of alkenes using different surrogate molecules. In contrast to previous hypotheses no carbon monoxide could be found during the reaction. Instead the reaction proceeds via the C-H activation of in situ generated methyl formate. On the basis of quantitative NMR experiments, a kinetic model involving all major intermediates is built which enables the knowledge-driven optimization of the reaction. Finally, a new reaction mechanism is proposed on the basis of in situ observed Pd-hydride, Pd-formyl and Pd-acyl species.

Exploring Structure and Function of Redox Intermediates in [NiFe]-Hydrogenases by an Advanced Experimental Approach for Solvated, Lyophilized and Crystallized Metalloenzymes.

To study metalloenzymes in detail, we developed a new experimental setup allowing the controlled preparation of catalytic intermediates for characterization by various spectroscopic techniques. The in situ monitoring of redox transitions by infrared spectroscopy in enzyme lyophilizate, crystals, and solution during gas exchange in a wide temperature range can be accomplished as well. Two O2 -tolerant [NiFe]-hydrogenases were investigated as model systems. First, we utilized our platform to prepare highly concentrated hydrogenase lyophilizate in a paramagnetic state harboring a bridging hydride. This procedure proved beneficial for 57 Fe nuclear resonance vibrational spectroscopy and revealed, in combination with density functional theory calculations, the vibrational fingerprint of this catalytic intermediate. The same in situ IR setup, combined with resonance Raman spectroscopy, provided detailed insights into the redox chemistry of enzyme crystals, underlining the general necessity to complement X-ray crystallographic data with spectroscopic analyses.

Probing Single-Atom Catalysts and Catalytic Reaction Processes by Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy.

Developing advanced characterization techniques for single-atom catalysts (SACs) is of great significance to identify their structural and catalytic properties. Raman spectroscopy can provide molecular structure information, and thus, the technique is a promising tool for catalysis. However, its application in SACs remains a great challenge because of its low sensitivity. We develop a highly sensitive strategy that achieves the characterization of the structure of SACs and in situ monitoring of the catalytic reaction processes on them by shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) for the first time. Using the strategy, Pd SACs on different supports were identified by Raman spectroscopy and the nucleation process of Pd species from single atoms to nanoparticles was revealed. Moreover, the catalytic reaction processes of the hydrogenation of nitro compounds on Pd SACs were monitored in situ, and molecular insights were obtained to uncover the unique catalytic properties of SACs. This work provides a new spectroscopic tool for the in situ study of SACs, especially at solid-liquid interfaces.

Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity.

CO2 reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H2 We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurcation between H2 and CO production on polycrystalline Au electrodes. Under the conditions of CO2 reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼0.2 and act as kinetically inert spectators. Electrokinetic data are consistent with a mechanism of CO production involving rate-limiting, single-electron transfer to CO2 with concomitant adsorption to surface active sites followed by rapid one-electron, two-proton transfer and CO liberation from the surface. In contrast, the data suggest an H2 evolution mechanism involving rate-limiting, single-electron transfer coupled with proton transfer from bicarbonate, hydronium, and/or carbonic acid to form adsorbed H species followed by rapid one-electron, one-proton, or H recombination reactions. The disparate proton coupling requirements for CO and H2 production establish a mechanistic basis for reaction selectivity in electrocatalytic fuel formation, and the high population of spectator CO species highlights the complex heterogeneity of electrode surfaces under conditions of fuel-forming electrocatalysis.

Application of Raman Spectroscopy to Working Gas Sensors: From in situ to operando Studies.

Understanding the mode of operation of gas sensors is of great scientific and economic interest. A knowledge-based approach requires the development and application of spectroscopic tools to monitor the relevant surface and bulk processes under working conditions (operando approach). In this review we trace the development of vibrational Raman spectroscopy applied to metal-oxide gas sensors, starting from initial applications to very recent operando spectroscopic approaches. We highlight the potential of Raman spectroscopy for molecular-level characterization of metal-oxide gas sensors to reveal important mechanistic information, as well as its versatility regarding the design of in situ/operando cells and the combination with other techniques. We conclude with an outlook on potential future developments.

Monitoring Reactions on Solid Phases with Raman Spectroscopy.

The benefits of Raman spectroscopy were shown for the on-bead monitoring of diverse reactions. Raman spectroscopy was used for the development of new procedures on established linker systems, the real-time observation of several reactions on solid phases and the estimation of the reaction time for a new cleavage strategy. Selected conversions on solid phases, such as the on-bead conversion of functional groups and the attachment of novel building blocks, were demonstrated. Raman spectra were obtained after isolation and purification of the solid supports, but they were also measured directly in the reaction vessels. Even the detection of Raman-active functional groups in swollen polymer resins and in reaction mixtures was demonstrated, and allows real-time observation of the progress of diverse reactions on solid supports.