Showing papers on "Raman spectroscopy published in 2021"

Power of Infrared and Raman Spectroscopies to Characterize Metal-Organic Frameworks and Investigate Their Interaction with Guest Molecules

Abstract: The variety of functionalities and porous structures inherent to metal-organic frameworks (MOFs) together with the facile tunability of their properties makes these materials suitable for a wide range of existing and emerging applications. Many of these applications are based on processes involving interaction of MOFs with guest molecules. To optimize a certain process or successfully design a new one, a thorough knowledge is required about the physicochemical characteristics of materials and the mechanisms of their interaction with guest molecules. To obtain such important information, various complementary analytical techniques are applied, among which vibrational spectroscopy (IR and Raman) plays an important role and is indispensable in many cases. In this review, we critically examine the reported applications of IR and Raman spectroscopies as powerful tools for initial characterization of MOF materials and for studying processes of their interaction with various gases. Both the advantages and the limitations of the technique are considered, and the cases where IR or Raman spectroscopy is preferable are highlighted. Peculiarities of MOFs interaction with specific gases and some inconsistent band assignments are also emphasized. Summarizing the broad analytical possibilities of the IR and Raman spectroscopies, we conclude that it can be applied in combinations with other techniques to explicitly establish the structure, properties, and reactivity of MOFs.

Raman spectroscopy for carbon nanotube applications

Abstract: The use of Raman spectroscopy for carbon nanotube applications is presented here as a tutorial review. After introducing the relevant basic aspects of Raman spectroscopy of graphene-related materials, we will discuss how to use the Raman spectral features for practical purposes of controlling and characterizing nanotube properties relevant for applied materials and devices. Advanced techniques with potential to enhance the relevance of Raman spectroscopy application in the carbon nanotube field are also presented.

Revealing the CO Coverage-Driven C-C Coupling Mechanism for Electrochemical CO 2 Reduction on Cu 2 O Nanocubes via Operando Raman Spectroscopy.

Abstract: Electrochemical reduction of carbon dioxide (CO2RR) is an attractive route to close the carbon cycle and potentially turn CO2 into valuable chemicals and fuels. However, the highly selective generation of multicarbon products remains a challenge, suffering from poor mechanistic understanding. Herein, we used operando Raman spectroscopy to track the potential-dependent reduction of Cu2O nanocubes and the surface coverage of reaction intermediates. In particular, we discovered that the potential-dependent intensity ratio of the Cu-CO stretching band to the CO rotation band follows a volcano trend similar to the CO2RR Faradaic efficiency for multicarbon products. By combining operando spectroscopic insights with Density Functional Theory, we proved that this ratio is determined by the CO coverage and that a direct correlation exists between the potential-dependent CO coverage, the preferred C-C coupling configuration, and the selectivity to C2+ products. Thus, operando Raman spectroscopy can serve as an effective method to quantify the coverage of surface intermediates during an electrocatalytic reaction.

New advances in using Raman spectroscopy for the characterization of catalysts and catalytic reactions

Abstract: Gaining insight into the mode of operation of heterogeneous catalysts is of great scientific and economic interest. Raman spectroscopy has proven its potential as a powerful vibrational spectroscopic technique for a fundamental and molecular-level characterization of catalysts and catalytic reactions. Raman spectra provide important insight into reaction mechanisms by revealing specific information on the catalysts' (defect) structure in the bulk and at the surface, as well as the presence of adsorbates and reaction intermediates. Modern Raman instrumentation based on single-stage spectrometers allows high throughput and versatility in design of in situ/operando cells to study working catalysts. This review highlights major advances in the use of Raman spectroscopy for the characterization of heterogeneous catalysts made during the past decade, including the development of new methods and potential directions of research for applying Raman spectroscopy to working catalysts. The main focus will be on gas-solid catalytic reactions, but (photo)catalytic reactions in the liquid phase will be touched on if it appears appropriate. The discussion begins with the main instrumentation now available for applying vibrational Raman spectroscopy to catalysis research, including in situ/operando cells for studying gas-solid catalytic processes. The focus then moves to the different types of information available from Raman spectra in the bulk and on the surface of solid catalysts, including adsorbates and surface depositions, as well as the use of theoretical calculations to facilitate band assignments and to describe (resonance) Raman effects. This is followed by a presentation of major developments in enhancing the Raman signal of heterogeneous catalysts by use of UV resonance Raman spectroscopy, surface-enhanced Raman spectroscopy (SERS), and shell-isolated nanoparticle surface-enhanced Raman spectroscopy (SHINERS). The application of time-resolved Raman studies to structural and kinetic characterization is then discussed. Finally, recent developments in spatially resolved Raman analysis of catalysts and catalytic processes are presented, including the use of coherent anti-Stokes Raman spectroscopy (CARS) and tip-enhanced Raman spectroscopy (TERS). The review concludes with an outlook on potential future developments and applications of Raman spectroscopy in heterogeneous catalysis.

Direct observation of two-dimensional magnons in atomically thin CrI3

Abstract: Magnons are collective spin excitations in crystals with long-range magnetic order. The emergent van der Waals magnets1–3 provide a highly tunable platform to explore magnetic excitations in the two-dimensional limit with intriguing properties, manifesting from their honeycomb lattice structure and switchable magnetic configurations. Here, we report the direct observation of two-dimensional magnons through magneto-Raman spectroscopy with optical selection rules determined by the interplay between crystal symmetry, layer number and magnetic states in atomically thin CrI3. In monolayers, we observe an acoustic magnon mode at ~0.3 meV. It has strict cross-circularly polarized selection rules locked to the magnetization direction that originates from the conservation of angular momentum of photons and magnons dictated by three-fold rotational symmetry4. Additionally, we reveal optical magnon modes at ~17 meV. This mode is Raman silent in monolayers, but optically active in bilayers and bulk due to a relaxation of the parity criterion resulting from the layer index. In the layered antiferromagnetic states, we directly resolve two degenerate optical magnon modes with opposite angular momentum and conjugate optical selection rules. From these measurements, we quantitatively extract the spin-wave gap, magnetic anisotropy and intralayer and interlayer exchange constants, and establish two-dimensional magnets as a new platform for exploring magnon physics. Magnons are collective excitations that dictate many of a magnet’s low-temperature properties. By means of Raman scattering, the magnon spectra of CrI3 are measured in the monolayer limit.

Perseverance’s Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) Investigation

Abstract: The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) is a robotic arm-mounted instrument on NASA’s Perseverance rover. SHERLOC has two primary boresights. The Spectroscopy boresight generates spatially resolved chemical maps using fluorescence and Raman spectroscopy coupled to microscopic images (10.1 μm/pixel). The second boresight is a Wide Angle Topographic Sensor for Operations and eNgineering (WATSON); a copy of the Mars Science Laboratory (MSL) Mars Hand Lens Imager (MAHLI) that obtains color images from microscopic scales (∼13 μm/pixel) to infinity. SHERLOC Spectroscopy focuses a 40 μs pulsed deep UV neon-copper laser (248.6 nm), to a ∼100 μm spot on a target at a working distance of ∼48 mm. Fluorescence emissions from organics, and Raman scattered photons from organics and minerals, are spectrally resolved with a single diffractive grating spectrograph with a spectral range of 250 to ∼370 nm. Because the fluorescence and Raman regions are naturally separated with deep UV excitation (<250 nm), the Raman region ∼ 800 – 4000 cm−1 (250 to 273 nm) and the fluorescence region (274 to ∼370 nm) are acquired simultaneously without time gating or additional mechanisms. SHERLOC science begins by using an Autofocus Context Imager (ACI) to obtain target focus and acquire 10.1 μm/pixel greyscale images. Chemical maps of organic and mineral signatures are acquired by the orchestration of an internal scanning mirror that moves the focused laser spot across discrete points on the target surface where spectra are captured on the spectrometer detector. ACI images and chemical maps (< 100 μm/mapping pixel) will enable the first Mars in situ view of the spatial distribution and interaction between organics, minerals, and chemicals important to the assessment of potential biogenicity (containing CHNOPS). Single robotic arm placement chemical maps can cover areas up to 7x7 mm in area and, with the < 10 min acquisition time per map, larger mosaics are possible with arm movements. This microscopic view of the organic geochemistry of a target at the Perseverance field site, when combined with the other instruments, such as Mastcam-Z, PIXL, and SuperCam, will enable unprecedented analysis of geological materials for both scientific research and determination of which samples to collect and cache for Mars sample return.

Sub-second Time-resolved Surface Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO2 Reduction on Copper.

Abstract: Electrocatalytic reduction of carbon dioxide (CO2) into value-added products (e.g., ethylene) is a promising approach for greenhouse gas mitigation, but many details of electrocatalytic CO2 reduction reactions (CO2RR) remain elusive. Raman spectroscopy is suitable for in situ characterization of CO2RR mechanisms, but the low signal intensity and resulting poor time resolution (often up to minutes) hampers the application of conventional Raman spectroscopy for the study of the dynamic CO2 reduction reaction, which requires sub-second time resolution. By using Time-Resolved Surface Enhanced Raman Spectroscopy (TR-SERS) we were able to successfully monitor CO2RR over Cu surfaces with sub-second time resolution. Anodic treatment at 1.55 V vs. the reversible hydrogen electrode (RHE) and subsequent surface oxide reduction (below -0.4 V vs. RHE) induced roughening of the Cu electrode surface, which resulted in hot-spots for TR-SERS, enhanced time resolution (down to ~ 0.7 s) and improved CO2RR efficiency (i.e., four-fold increase in ethylene faradaic efficiency). With TR-SERS, the initial formation of hot-spots for SERS and CO2RR was followed (<7 s), after which a stable copper surface surrounded by increased local alkalinity was formed. Our measurements revealed that a highly dynamic CO intermediate, with a characteristic vibration below 2060 cm-1, is related to C-C coupling and ethylene production (-0.9 V vs. RHE), whereas lower cathodic bias (-0.7 V vs. RHE) resulted in gaseous CO production from isolated and static CO surface species with a distinct vibration at 2092 cm-1. Our results provide valuable time-resolved insights into the dynamic nature of the electrode surface and adsorbed intermediates during CO2 electrochemical reduction on copper and showcase the potential of TR-SERS in copper-based electrocatalysis to follow reaction dynamics.

Asymmetric Triple-Atom Sites Confined in Ternary Oxide Enabling Selective CO2 Photothermal Reduction to Acetate.

Abstract: Light-induced heat is largely neglected in traditional photocatalytic systems, especially for the thermodynamically and kinetically challenging CO2 reduction to C2 fuels. Herein, we first design asymmetric Metal1-O-Metal2 triple-atom sites confined in phenakite to facilitate C-C coupling and employ photoinduced heat to increase molecular thermal vibration and accelerate CO2 reduction to C2 fuels. Using O-vacancy-rich Zn2GeO4 nanobelts as prototypes, quasi in situ Raman spectra disclose the Zn-O-Ge triatomic sites are likely the reactive sites. Density functional theory calculations reveal that the asymmetric Zn-O-Ge sites could promote C-C coupling through inducing distinct charge distributions of neighboring C1 intermediates, whereas the created O vacancies could lower the energy barrier of the rate-determining hydrogenation step from 1.46 to 0.67 eV. Catalytic performances under different testing conditions demonstrate that light initiates the CO2 reduction reaction. In situ Fourier-transform infrared spectra and D2O kinetic isotopic effect experiments disclose that light-induced heat kinetically triggers C-C coupling and accelerates OCCO* hydrogenation via providing abundant hydrogen species. Consequently, in a simulated air atmosphere under 0.1 W/cm2 illumination at 348 K, the O-vacancy-rich Zn2GeO4 nanobelts demonstrate an acetate output of 12.7 μmol g-1 h-1, a high acetate selectivity of 66.9%, a considerable CO2-to-CH3COOH conversion ratio of 29.95%, and a stability of up to 220 h.

Critical Impact of Nitrogen Vacancies in Nonradical Carbocatalysis on Nitrogen-Doped Graphitic Biochar.

Abstract: Nitrogen-doped graphitic biochar (NBC) has boosted the development of nonradical peroxymonosulfate (PMS) activation in environmental remediation. However, the specific role of nitrogen species played in NBC-based nonradical carbocatalysis remains vaguely interpreted. To pinpoint the critical nitrogen speciation, a sophisticated thermo-mechanochemical manipulation was exploited to prepare a series of NBCs with similar dimensional structures and oxygen levels but different nitrogen species (i.e., dopants and vacancies). Different from conventional perspectives, nonradical NBC-based carbocatalysis was found to be preferably determined by the nitrogen vacancies more than their parent nitrogen dopants. Raman depth analysis evidenced that a complete transformation of nitrogen dopants into nitrogen vacancies could be achieved at 800 °C, where an excellent nonradical abatement of 4-chlorophenol (4-CH, 90.9% removal) was found for the NBC800 with a low PMS consumption (1.24 mM). According to PMS adsorption experiments, nitrogen vacancies exhibited the highest affinity toward the PMS molecules compared to nitrogen dopants, which accounted for the superior carbocatalysis. Electron paramagnetic resonance and Raman spectroscopic analyses indicated that the original PMS molecules were bound to positively charged nitrogen vacancies, and a robust metastable complex (*HSO5-) evolved subsequently via hydrogen abstraction by adjacent persistent free radicals. In situ Raman techniques could be adopted to estimate the level of nitrogen vacancies associated with the polarization of electron distribution. The flexible feature and practical prospects of nitrogen vacancy-based carbocatalysis were also observed in the remediation of simulated phenolic industrial wastewater. Overall, this study unravels the dilemma in the current NBC-based nonradical carbocatalysis and advances our understanding of nitrogen doping technology for next-generation biochar design.

Surface-Enhanced Raman Spectroscopic Evidence of Key Intermediate Species and Role of NiFe Dual-Catalytic Center in Water Oxidation

Abstract: NiFe-based electrocatalysts have attracted great interests due to the low price and high activity in oxygen evolution reaction (OER). However, the complex reaction mechanism of NiFe-catalyzed OER has not been fully explored yet. Detection of intermediate species can bridge the gap between OER performances and catalyst component/structure properties. Here, we performed label-free surface-enhanced Raman spectroscopic (SERS) monitoring of interfacial OER process on Ni3 FeOx nanoparticles (NPs) in alkaline medium. By using bifunctional Au@Ni3 FeOx core-satellite superstructures as Raman signal enhancer, we found direct spectroscopic evidence of intermediate O-O- species. According to the SERS results, Fe atoms are the catalytic sites for the initial OH- to O-O- oxidation. The O-O- species adsorbed across neighboring Fe and Ni sites experiences further oxidation caused by electron transfer to NiIII and eventually forms O2 product.

Spatially offset Raman spectroscopy for biomedical applications

Abstract: In recent years, Raman spectroscopy has undergone major advancements in its ability to probe deeply through turbid media such as biological tissues. This progress has been facilitated by the advent of a range of specialist techniques based around spatially offset Raman spectroscopy (SORS) to enable non-invasive probing of living tissue through depths of up to 5 cm. This represents an improvement in depth penetration of up to two orders of magnitude compared to what can be achieved with conventional Raman methods. In combination with the inherently high molecular specificity of Raman spectroscopy, this has therefore opened up entirely new prospects for a range of new analytical applications across multiple fields including medical diagnosis and disease monitoring. This article discusses SORS and related variants of deep Raman spectroscopy such as transmission Raman spectroscopy (TRS), micro-SORS and surface enhanced spatially offset Raman spectroscopy (SESORS), and reviews the progress made in this field during the past 5 years including advances in non-invasive cancer diagnosis, monitoring of neurotransmitters, and assessment of bone disease.

Activation Strategy of MoS2 as HER Electrocatalyst through Doping-Induced Lattice Strain, Band Gap Engineering, and Active Crystal Plane Design

Abstract: Doping engineering emerges as a contemporary technique to investigate the catalytic performance of MoS2. Cation and anion co-doping appears as an advanced route toward electrocatalytic hydrogen evolution reaction (HER). V and N as dopants in MoS2 (VNMS) build up a strain inside the crystal structure and narrow down the optical band gaps manifesting the shifting of the absorbance band toward lower energy and improved catalytic performance. FE-SEM, HR-TEM, and XRD analysis confirmed that V and N doping decreases agglomeration possibility, particle size, developed strain, and crystal defects during crystal growth. Frequency shift and peak broadening in Raman spectra confirmed the doping induced strain generation in MoS2 leading to the modification of acidic and alkaline HER (51 and 110 mV @ 10 mAcm-2, respectively) performance. The improved donor density in VNMS was confirmed by the Mott-Schottky analysis. Enhanced electrical conductivity and optimized electronic structures facilities H* adsorption/desorption in the catalytically active (001) plane of cation and anion co-doped MoS2.

A Comprehensive Review on Raman Spectroscopy Applications

Abstract: Raman spectroscopy is a very powerful tool for material analysis, allowing for exploring the properties of a wide range of different materials. Since its discovery, Raman spectroscopy has been used to investigate several features of materials such carbonaceous and inorganic properties, providing useful information on their phases, functions, and defects. Furthermore, techniques such as surface and tip enhanced Raman spectroscopy have extended the field of application of Raman analysis to biological and analytical fields. Additionally, the robustness and versatility of Raman instrumentations represent a promising solution for performing on-field analysis for a wide range of materials. Recognizing the many hot applications of Raman spectroscopy, we herein overview the main and more recent applications for the investigation of a wide range of materials, such as carbonaceous and biological materials. We also provide a brief but exhaustive theoretical background of Raman spectroscopy, also providing deep insight into the analytical achievements.

From NiMoO4 to γ-NiOOH: Detecting the Active Catalyst Phase by Time Resolved in Situ and Operando Raman Spectroscopy.

Abstract: Water electrolysis powered by renewable energies is a promising technology to produce sustainable fossil free fuels. The development and evaluation of effective catalysts are here imperative; however, due to the inclusion of elements with different redox properties and reactivity, these materials undergo dynamical changes and phase transformations during the reaction conditions. NiMoO4 is currently investigated among other metal oxides as a promising noble metal free catalyst for the oxygen evolution reaction. Here we show that at applied bias, NiMoO4·H2O transforms into γ-NiOOH. Time resolved operando Raman spectroscopy is utilized to follow the potential dependent phase transformation and is collaborated with elemental analysis of the electrolyte, confirming that molybdenum leaches out from the as-synthesized NiMoO4·H2O. Molybdenum leaching increases the surface coverage of exposed nickel sites, and this in combination with the formation of γ-NiOOH enlarges the amount of active sites of the catalyst, leading to high current densities. Additionally, we discovered different NiMoO4 nanostructures, nanoflowers, and nanorods, for which the relative ratio can be influenced by the heating ramp during the synthesis. With selective molybdenum etching we were able to assign the varying X-ray diffraction (XRD) pattern as well as Raman vibrations unambiguously to the two nanostructures, which were revealed to exhibit different stabilities in alkaline media by time-resolved in situ and operando Raman spectroscopy. We advocate that a similar approach can beneficially be applied to many other catalysts, unveiling their structural integrity, characterize the dynamic surface reformulation, and resolve any ambiguities in interpretations of the active catalyst phase.

A Tandem (Bi2O3 → Bimet) Catalyst for Highly Efficient ec-CO2 Conversion into Formate: Operando Raman Spectroscopic Evidence for a Reaction Pathway Change

Abstract: A novel bismuth oxide nanofoam, produced by means of the dynamic hydrogen bubble template (DHBT) electrodeposition approach followed by thermal annealing at 300 °C for 12 h, demonstrates excellent ...

Gain/noise figure spectra of average power model Raman optical amplifiers in coarse wavelength multiplexed systems

Abstract: This work clarifies the gain/noise figure spectra of average power model Raman optical amplifiers in coarse wavelength multiplexed systems. The proposed model have a total received power of 16.306 dBm, signal gain of 21.68 dB, and noise figure of 3.802 dB at the same operation parameters of the previous model which operated at length 0.2 km at the optical fiber coarse wavelength division multiplexing (CWDM) and transmitted signal power is 20 dBm. So the updates help us to greatly improve the system.

Raman spectrum of Janus transition metal dichalcogenide monolayers WSSe and MoSSe

Abstract: Janus transition metal dichalcogenides (TMDs) lose the horizontal mirror symmetry of ordinary TMDs, leading to the emergence of additional features, such as native piezoelectricity, Rashba effect, and enhanced catalytic activity While Raman spectroscopy is an essential nondestructive, phase- and composition-sensitive tool to monitor the synthesis of materials, a comprehensive study of the Raman spectrum of Janus monolayers is still missing Here, we discuss the Raman spectra of WSSe and MoSSe measured at room and cryogenic temperatures, near and off resonance By combining polarization-resolved Raman data with calculations of the phonon dispersion and using symmetry considerations, we identify the four first-order Raman modes and higher-order two-phonon modes Moreover, we observe defect-activated phonon processes, which provide a route toward a quantitative assessment of the defect concentration and, thus, the crystal quality of the materials Our work establishes a solid background for future research on material synthesis, study, and application of Janus TMD monolayers

Tetrathiafulvalene-based covalent organic frameworks for ultrahigh iodine capture

Abstract: To safeguard the development of nuclear energy, practical techniques for capture and storage of radioiodine are of critical importance but remain a significant challenge. Here we report the synergistic effect of physical and chemical adsorption of iodine in tetrathiafulvalene-based covalent organic frameworks (COFs), which can markedly improve both iodine adsorption capacity and adsorption kinetics due to their strong interaction. These functionalized architectures are designed to have high specific surface areas (up to 2359 m2 g−1) for efficient physisorption of iodine, and abundant tetrathiafulvalene functional groups for strong chemisorption of iodine. We demonstrate that these frameworks achieve excellent iodine adsorption capacity (up to 8.19 g g−1), which is much higher than those of other materials reported so far, including silver-doped adsorbents, inorganic porous materials, metal–organic frameworks, porous organic frameworks, and other COFs. Furthermore, a combined theoretical and experimental study, including DFT calculations, electron paramagnetic resonance spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy, reveals the strong chemical interaction between iodine and the frameworks of the materials. Our study thus opens an avenue to construct functional COFs for a critical environment-related application.