Spectroscopy Experiments Research Articles

Progress of mechanistic pathways involved in electrochemical CO2 reduction

The electrochemical reduction of carbon dioxide (CO2) into value-added chemicals and fuels has been extensively studied as a promising strategy for mitigating environmental issues and achieving sustainable energy conversion. Substantial efforts have been made to improve the understanding of CO2 reduction reaction (CO2RR) mechanisms by computational and spectroscopic studies. An in-depth understanding of CO2RR mechanism can provide the guidance and criteria for designing high-efficiency catalysts, and hence, steering CO2RR to desired products. This review systematically discusses the formation mechanisms and reaction pathways of various CO2RR products, including C1 products (CO, HCOOH, and CH4), C2 products (C2H4, C2H5OH, and CH3COOH), and C3+ products (C3H6, C3H7OH, and others). The reaction pathways are elucidated by analyzing the adsorption behavior, energy barriers, and intermediate coupling steps involved in the generation of each product. Particular emphasis is placed on the key intermediates, such as *OCHO, *COOH, *CO, *OCCOH, and *CCO, which play crucial roles in determining the product selectivity. The effects of catalyst composition, morphology, and electronic structure on the adsorption and activation of these intermediates are also discussed. Moreover, advanced characterization techniques, including in-situ spectroscopy and isotopic labeling experiments, are highlighted for their contributions to unraveling the reaction mechanisms. The review aims to provide critical insights to reveal the activity-determining parameters and underlying CO2RR mechanisms, which will guide the rational design of next-generation electrocatalysts for selective CO2RR towards high-value products.

Synthesis and anion binding properties of (thio)urea functionalized Ni(II)-salen complexes.

Salen ligands (salen = N,N'-ethylenebis(salicylimine)) are well-known for their versatility and widespread utility in chelating metal complexes. However, installation of hydrogen-bonding units on the salen framework, particularly functional groups that require amine-based precursors such as (thio)ureas, is difficult to achieve without the use of protecting group strategies. In this report, we show that the phenylketone analog of salicyladehyde is a stable alternative that enables the facile installation of hydrogen bonding (thio)urea groups on the salen scaffold, thus imparting anion binding abilities to a metal salen complex. Synthesis of symmetric N-phenyl(thio)urea salen ligands functionalized at the 3,3'-position and an unsymmetric salen ligand with N-phenylurea at the 5-position was achieved. Subsequent metalation with nickel(II) acetate afforded the nickel(II) complexes that were investigated for their anion binding properties towards F-, Cl-, Br-, CH3COO-, and H2PO4-. Solid-state structures of the nickel(II) complexes as well as the Cl- bound dimer of the symmetric urea complex were obtained. The unusual acidity of the (thio)urea groups is reflected in the pKa-dependent anion binding behavior of the nickel(II) complexes, as elucidated by 1H and 19F Nuclear Magnetic Resonance (NMR) spectroscopy and Diffusion Ordered Spectroscopy (DOSY) experiments.

Anchoring AuCu alloy nanoparticles on TiO2 nanosheets: Exploiting synergistic effects and directed electron transfer for enhanced photocatalytic H2 evolution

AuCu/TiO2 composite photocatalysts were prepared by anchoring AuCu nanoparticles (NPs) on TiO2 nanosheets using a simple photoreduction method. Visible diffuse reflectance spectra indicated that the AuCu/TiO2 significantly enhanced light absorption in the visible region. Through photoluminescence spectroscopy and steady-state surface photovoltage experiments, AuCu/TiO2 exhibits an excellent photogenerated electron transfer rate. In addition, photoelectrochemical experiments showed that AuCu/TiO2 had a high photogenerated charge separation efficiency. AuCu/TiO2 (1.0 wt%) exhibited the best performance, under full spectrum, the hydrogen evolution rate is 33.94 mmol g−1 h−1, which is 1.59 times and 1.66 times higher than that of single metal Au/TiO2 (1.0 wt%) (21.28 mmol g−1 h−1) and Cu/TiO2 (1.0 wt%) (20.42 mmol g−1 h−1), respectively. The results showed that AuCu NPs greatly enhanced the photocatalytic performance of the composite photocatalysts.

Asymmetric conformation of the high-spin state of iron(II)-tris(2,2-bipyridine): Time-resolved x-ray absorption and ultraviolet circular dichroism.

We analyze the structures of the low-spin (LS) ground state and the high-spin (HS) lowest excited state of the iron-(II)-tris bipyridine complex ([Fe(bpy)3]2+) using density functional theory PBE methods, modeling the solvent interactions with conductor-like polarizable continuum model. These calculations are globally benchmarked against a wide range of experimental observables that include ultraviolet-visible linear absorption and circular dichroism (CD) spectra and Fe K-edge x-ray absorption near edge spectra (XANES). The calculations confirm the already established D3 geometry of the LS state, as well as a departure from this geometry for the HS state, with the appearance of inequivalent Fe-N bond elongations. The simulated structures nicely reproduce the above-mentioned experimental observables. We also calculate the vibrational modes of the LS and HS states. For the former, they reproduce well the vibrational frequencies from published infrared and Raman data, while for the latter, they predict very well the low-frequency vibrational coherences, attributed to Fe-N stretch modes, which were reported in ultrafast spectroscopic experiments. We further present calculations of the high-frequency region, which agree with recent ultrafast transient infrared spectroscopy studies. This work offers a common basis to the structural information encoded in the excited state CD and the Fe K XANES of the HS state tying together different structural IR, UV-visible, and x-ray observables.

Revealing a new mechanism of stable intersolubility of methanol-n-heptane blended fuel assisted by co-solvents at the microscopic molecular level: Insights and validation from quantum chemical simulation

Methanol, a promising green alternative to traditional fossil fuels, requires blending with high-energy fuels or additives due to its low energy density and cetane number. However, methanol’s high polarity often causes phase separation with other fuels, hindering its widespread use. Adding suitable co-solvents is a known method to address phase separation in fuel blends. For the first time, this study aims to reveal the microscopic molecular mechanism by which butanol, as a co-solvent, can improve the miscibility stability of methanol-gasoline blends. To simplify the analysis in this study, n-heptane, which is a single-component fuel was used as a representative of the multi-component gasoline. Firstly, experimental tests were conducted to investigate the miscibility of different blend ratios of methanol-n-heptane under the influence of different butanol isomers. Secondly, molecular simulation research through the Gaussian and Multiwfn software. Next, through Fourier transform infrared spectroscopy, the mutual solubility of ternary blends was studied. The results showed that the addition of butanol, particularly n-butanol (in comparison to isobutanol), could effectively stabilize the miscibility of anhydrous methanol and n-heptane. Molecular conformation simulations and infrared spectroscopy experiments revealed that the presence of butanol restructures the electrostatic interactions (hydrogen bonding) on the surface of methanol molecules, shielding their polarity. This allows the butanol and methanol molecules to associate more like non-polar species, enhancing their interaction with n-heptane through van der Waals forces, thereby improving the overall miscibility stability of the methanol and n-heptane. These findings offer new insights into the micro-molecular miscibility mechanism of methanol-gasoline blends, which is essential for the successful application of methanol as an alternative fuel.

Biodegradable MAM-based amphiphilic block copolymers: Toward efficient and eco-friendly kinetic inhibitors for methane hydrate formation

The development of low dosage hydrate inhibitors holds significant implications for the oil and gas industry. Some commercially available inhibitors, such as Luvicap EG, are derived from the lactam-containing polymer PVCap, which exhibit limited biodegradability and possess low cloud point (30-40℃), thereby constraining their practical utility. The present study successfully synthesized a series of novel amphiphilic block copolymers based on methacrylamide (MAM) by introducing biodegradable hydrophobic esters (ε-caprolactone (CL), δ-valerolactone (VL), and glycolide (GA)) onto the main chain of poly (methyl acrylamide) (PMAM), serving as KHIs. The synthesized MAM-based polymers maintain water solubility within the range of 0–98 ℃ without thermal responsiveness, effectively preventing deposition issues associated with traditional KHIs. Additionally, all MAM-based polymers demonstrated good biodegradability. The dynamics experiments have shown that PMAM homopolymers did not possess KHI effect, while the MAM-based block copolymers, especially PMAM-b-PVL, exhibited excellent performance in inhibiting hydrate nucleation. At low concentrations, the KHI effect of PMAM-b-PVL was comparable to that of the commercial KHI Luvicap EG. The in-situ Raman spectroscopy experiment further revealed the inhibition mechanism of the amphiphilic polymers, which was achieved by forming effective arrangements at the gas–liquid interface and disrupting the water structure in the interfacial region, thereby impeding the formation of hydrate cages, especially large cages. The findings provided a promising and environmentally friendly solution for the management of hydrates in the oil and gas industry

Selective monodeuteration enabled by bisphosphonium catalyzed ring opening processes

The selective incorporation of a deuterium atom into small molecules with high selectivity is highly valuable for medical and chemical research. Unfortunately, this remains challenging due to the complete deuteration caused by commonly used hydrogen isotope exchange strategies. We report the development of a photocatalytic selective monodeuteration protocol utilizing C–C bond as the unconventional functional handle. The synergistic combination of radical-mediated C–C bond scission and deuterium atom transfer processes enables the effective constructions of benzylic CDH moieties with high selectivity for monodeuteration. The combinational use of a bisphosphonium photocatalyst, thiol catalyst, and CH3OD deuteration agent provides operationally simple conditions for photocatalytic monodeuteration. Moreover, the photoinduced electron transfer process of the bisphosphonium photocatalyst is elucidated through a series of spectroscopy experiments, identifying a peculiar back electron transfer process that can be regulated by subsequent nucleophilic additions.

Signatures of coherent vibrational dynamics in ethylene carbonate.

Despite having practical applications in battery technology and serving as a model system for Fermi resonance coupling, ethylene carbonate (EC) receives little direct attention as a vibrational probe in nonlinear vibrational spectroscopy experiments. EC contains a Fermi resonance that is well-characterized in the linear spectrum, and the environmental sensitivity of its Fermi resonance peaks could make it a good molecular probe for two-dimensional infrared spectroscopy (2DIR) experiments. As a model system, we investigate the linear and 2DIR vibrational spectrum of the carbonyl stretching region of ethylene carbonate in tetrahydrofuran. The 2DIR spectrum reveals peak dynamics that evolve coherently. We characterize these dynamics in the context of Redfield theory and find evidence that EC dynamics proceed through coherent pathways, including singular coherence transfer pathways that have not been widely observed in other studies. We find that coherent contributions play a significant role in the observed dynamics of cross-peaks in the 2DIR spectrum, which must be accounted for to extract accurate measurements of early waiting time dynamics.

Selective Monoborylation of Methane by a Mono Bipyridyl‐Nickel(II) Hydride Catalyst

We report the development of an earth‐abundant metal catalyst for methane C‒H borylation. The post‐synthetic metalation of bipyridine‐functionalized zirconium metal−organic framework (MOF) with NiBr2, followed by treatment of NaEt3BH affords MOF‐supported monomeric bipyridyl‐nickel(II) dihydride species via active site isolation. The heterogeneous and recyclable nickel catalyst selectively borylates methane at 200 ºC using pinacolborane (HBpin) to afford CH3Bpin in 61% yield with a turnover number (TON) up to 1388. The confinement of the active NiH2‐species within the uniformly porous MOF allows selective monoborylation of methane via shape‐selective catalysis by preventing the formation of sterically encumbered overborylated products. Unlike MOF‐Ni catalyst, its homogeneous control is almost inactive in methane borylation due to its intermolecular decomposition. Our mechanistic investigation, including spectroscopic, kinetic, and control experiments, as well as DFT calculations, revealed that stabilizing mononuclear bipyridyl‐nickel dihydride and diboryl species by MOF is crucial for achieving efficient methane borylation via turnover‐limiting σ‐bond metathesis. This work shows promise in designing MOF‐based abundant metal catalysts for the chemoselective functionalization of methane and other inert molecules into valuable chemicals.

Selective Monoborylation of Methane by a Mono Bipyridyl-Nickel(II) Hydride Catalyst.

We report the development of an earth-abundant metal catalyst for methane C-H borylation. The post-synthetic metalation of bipyridine-functionalized zirconium metal-organic framework (MOF) with NiBr2, followed by treatment with NaEt3BH affords MOF-supported monomeric bipyridyl-nickel(II) dihydride species via active site isolation. The heterogeneous and recyclable nickel catalyst selectively borylates methane at 200 °C using pinacolborane (HBpin) to afford CH3Bpin in 61 % yield with a turnover number (TON) up to 1388. The confinement of the active NiH2-species within the uniformly porous MOF allows selective monoborylation of methane via shape-selective catalysis by preventing the formation of sterically encumbered overborylated products. Unlike MOF-Ni catalyst, its homogeneous control is almost inactive in methane borylation due to its intermolecular decomposition. Our mechanistic investigation, including spectroscopic, kinetic, and control experiments, as well as DFT calculations, revealed that stabilizing mononuclear bipyridyl-nickel dihydride and diboryl species by MOF is crucial for achieving efficient methane borylation via turnover-limiting σ-bond metathesis. This work shows promise in designing MOF-based abundant metal catalysts for the chemoselective functionalization of methane and other inert molecules into valuable chemicals.

Spectrum Broadening Due to Nonselective Linear Absorption

The position and linewidth of an emission spectrum reflect the physical properties of the luminophor. So, keeping the spectrum from distortion is very important in its measurement. However, we find that the spectrum linewidth will be broadened when the near-infrared radiation from a sodium lamp passes through a nonselective linear absorbing filter. This counterintuitive linewidth-broadening phenomenon is obvious when the residual light power after the filter is low enough, typically lower than 2.48×10−4 μW. This novel linewidth-broadening effect is different from the well-known Lorentzian, Doppler, and Voigt broadening, and is likely to be more independent evidence of the discrete wavelet structure of classical plane light waves. The effect is significant in high-sensitivity spectroscopy measurements, for example streak camera spectroscopy and Raman spectroscopy experiments. In addition, this effect may also be significant for cosmological research.

Quasi-1D Oxides as Electrocatalysts for Water-Splitting: Case Study of Sr9M2Mn5O21 (M = Co, Ni, Cu, Zn).

We have demonstrated that multimetal oxides with a quasi-1D structure can be effective electrocatalysts for water electrolysis. Four materials have been systematically investigated, namely, Sr9Co2Mn5O21, Sr9Ni2Mn5O21, Sr9Cu2Mn5O21, and Sr9Zn2Mn5O21, comprising 1D chains of face-sharing MnO6 octahedra and MO6 trigonal prisms (M = Co, Ni, Cu or Zn), which are held together by strontium ions located between the chains. These materials show a consistent trend in electrocatalytic properties for both half-reactions of water-splitting, i.e., oxygen evolution and hydrogen evolution reactions (OER and HER). In particular, Sr9Ni2Mn5O21 has an outstanding performance for OER, with an overpotential of 0.37 V, which is lower than those of many 3D and 2D oxides, and rivals the activity of noble metal catalysts, such as RuO2. This is important given that the OER is considered the bottleneck of the water-slitting process. Chronopotentiometry studies, combined with X-ray photoelectron spectroscopy (XPS) and X-ray diffraction experiments pre- and post-reaction, indicate that Sr9Ni2Mn5O21 is highly stable and retains its structural integrity upon electrocatalytic reactions. This study highlights the potential of quasi-1D oxides as active electrocatalysts for water-splitting.

In vitro spectroscopic analysis of the chemical interaction between calcium hypochlorite and chlorhexidine.

This study aimed to identify the chemical composition resulting from the chemical interaction between calcium hypochlorite [Ca(OCl)2] and chlorhexidine (CHX) using different 1H and 13C nuclear magnetic resonance spectrometry (NMR), correlated two-dimensional spectroscopy (2D COSY), heteronuclear single quantum coherence (HSQC), and Fourier Transform Infrared Spectroscopy (FTIR) experiments. The 5.25% Ca(OCl)2 was mixed with 2% CHX in a 1:1 ratio, obtaining an orange-brown precipitate that was filtered, washed in ultrapure water, dried and characterized by 1H and 13C NMR, 2D COSY, HSQC and FTIR. One-dimensional and two-dimensional NMR spectra demonstrated the chemical changes around the protons and carbon atoms of the initial CHX and after reacted with Ca(OCl)2. These techniques and FTIR show that the interaction generated two by-products from the degradation of CHX, none of which were parachloroaniline (PCA) despite both products obtained being substituted benzene compounds. Using NMR and FTIR data together with a previously proposed catalytic cleavage degradation mechanism for CHX, the products appear to be parachlorophenylurea (PCU) and parachlorophenylguanidyl-1,6-diguanidyl-hexane (PCGH). Therefore, this in vitro study demonstrated that the precipitate formed from the chemical interaction between Ca(OCl)₂ and CHX results in two by-products, PCU and PCGH, neither of which is PCA. Due to the absence of cytotoxicity studies on the products generated from the combination of Ca(OCl)₂ and CHX, an intermediate rinse with an inert solution is recommended to remove these compounds from the root canals.

Status of laser spectroscopy measurements of long-lived antiprotonic and pionic helium atoms at CERN and PSI

The results of laser spectroscopy experiments of antiprotonic helium atoms carried out at the Antiproton Decelerator of CERN, and pionic helium atoms measured at the 590[Formula: see text]MeV ring cyclotron facility of the Paul Scherrer Institute are reviewed. The former experiment determined the antiproton-to-electron mass ratio as [Formula: see text]. In the latter, a resonant transition [Formula: see text] of pionic helium at a frequency of [Formula: see text][Formula: see text]GHz was detected. Some future perspectives are briefly described.

Generalised hydrogen interactions with CINCO: a window to new physics

We present semi-analytic solutions for atomic transition rates in hydrogenic atoms induced by scalar, pseudoscalar, vector, axial-vector, and tensor interactions. Our results agree with quantum electrodynamics predictions to ~ 0.005 % precision, and further allow us to calculate absorption and emission rates for axions, hidden photons, light scalars or other dark matter candidates for hydrogen and hydrogenic ions. These results can be used to inform searches for light new physics as well as in calculations relevant to searches for fifth forces or varying fundamental constants, with applications from astrophysics to laboratory spectroscopy experiments. We also provide a dedicated tool for the construction of hydrogenic transition amplitudes: “Computation of hydrogen radial INtegrals and COefficients” (CINCO).

Evidence for Distinct Active Sites on Oxide-Derived Cu for Electrochemical Nitrate Reduction.

Cu is a promising catalyst for electrochemical nitrate (NO3-) reduction. However, desorption of the nitrite (NO2-) intermediate can occur, leading to lowered ammonia productivity and Faradaic efficiency. Here, we discovered that this does not occur with oxide-derived Cu due to the presence of at least two distinct types of cooperative active sites: one for NO3- → NO2- and another for NO2- → NH3. As a result, oxide-derived Cu exhibits enhanced ammonia productivity with a mixed NO3-/NO2- feed relative to pure NO3- or NO2-. In contrast, this was not observed with a standard Cu sample, implying the presence of only a single type of active site. Our dual-site hypothesis was supported by attenuated total reflection surface enhanced infrared absorption spectroscopy and isotopic labeling experiments involving co-reduction of 15NO3-/14NO2-. We also successfully simulated our experimental results using a mathematical model involving two different adsorption sites. These findings motivate the need for further study and rational design of such active sites.

Unveiling Doppler effects and charge phenomena in the elastic scattering of keV electrons on polystyrene

Recoil energy is a phenomenon that is observed in various spectroscopy experiments. Elastic Peak Electron Spectroscopy (also known as Electron Compton Scattering) studies the shape of the elastic peak resulting from electron scattering from solid targets. As the atoms move around their equilibrium position, they scatter the distribution of recoil energies, resulting in a broadening of the elastic peak known as Doppler broadening. Since the hydrogen peak has the largest recoil energy shifts due to the low mass of hydrogen, Elastic Peak Electron Spectroscopy is ideal for the detection of hydrogen. The most important aspects of this method for the detection of hydrogen include electron-induced hydrogen desorption and, in dielectric materials, charge phenomena. This work focuses on the elastic peak spectra of keV electrons impinging on polystyrene, with particular interest in the changes in line shape due to the Doppler effect and surface charge during electron irradiation.

Deciphering Spectroscopic Signatures of Competing Ca2+ - Peptide Interactions.

Calcium-protein interactions are of paramount importance in biochemistry. They are a key element in a number of biological processes, such as neuronal signaling. Therefore, an understanding of the interaction at the molecular level is highly desirable. Here, we study the zwitterionic model peptide l-alanyl-l-alanine (2Ala), which has two distinct and competing binding sites for Ca2+: The carbonyl of the peptide bond and the C-terminus, the carboxylate group. We perform linear and two-dimensional IR spectroscopy experiments and find that the spectroscopic signatures of both moieties in the IR spectra change in amplitude and peak position upon the addition of CaCl2: A blueshift of the asymmetric carboxylate band and a redshift for the amide I mode. Ab initio molecular dynamics simulations confirm the direct interaction of the Ca2+ ion at both the carboxylate and the amide CO site leading to different spectral responses. The blueshift of the asymmetric carboxylate band is caused by a localization of the charge, leading to a decoupling of the CO stretching modes of the carboxylate group. The slight redshift of the amide I mode of 2Ala upon the addition of CaCl2 contrasts the blueshift that has been observed for isolated amide motifs, such as N-methylacetamide (NMA). This difference is caused by the smaller number of water molecules being replaced by the Ca2+ ion for 2Ala's amide compared to less sterically hindered, isolated amide carbonyls, in conjunction with vibrational Stark effects. Our results highlight the importance of considering potential competing binding sites, such as the amide CO backbone, the termini and residues, as well as the nature of the hydration of both peptide and ion, when exploring ions' interacting with small peptides and larger proteins.

Fabrication and characterization of lysozyme fibrils/Zein complexes for resveratrol encapsulation: Improving stability, antioxidant and antibacterial activities

Resveratrol (Res), a naturally occurring hydrophobic polyphenol, boasts numerous health-promoting bio-functionalities. However, its limited water solubility and stability impede further applications in the food industry. This study aims to address these challenges by fabricating stable Res-loaded lysozyme fibrils/zein (Ly-F/Z) complexes. The complexes were prepared using an antisolvent precipitation method. The interaction mechanism between Ly-F and zein was elucidated through dynamic light scattering, Fourier-transform infrared spectroscopy and dissociative experiments, revealing the involvement of hydrogen bonding, electrostatic forces and hydrophobic interactions in complex formation. The Ly-F/Z complexes were utilized to encapsulate Res, resulting in an encapsulation efficiency of 82.58 %. X-ray diffraction analysis confirmed the successful encapsulation of Res within Ly-F/Z complexes, presenting an amorphous state. The Ly-F/Z-Res complexes exhibited a “fruit tree” morphology with dense fruit, showcasing remarkable stability, antioxidant and antibacterial activities. Consequently, the Ly-F/Z complexes can serve as promising delivery systems for Res in functional foods.

Isolation and Characterization of Stigmasterol from Psidium guajava Leaves: A Promising Bioactive Compound with Therapeutic Potential

This study aimed to isolate and characterize bioactive compounds from the leaves of Psidium guajava Linn. The hydroethanolic extract yielded 32% (80 g) from the crude material, which was subjected to column chromatography for fractionation. Structural elucidation of the isolated compound was performed using 1D and 2D Nuclear Magnetic Resonance (NMR) spectroscopy, including COSY, HSQC, and HMBC experiments. The spectral data confirmed the presence of stigmasterol, characterized by its distinct chemical shifts and long-range correlations between carbon and proton atoms. Stigmasterol was isolated as a white, crystalline solid and identified by its unique physio-chemical properties, such as solubility in organic solvents, a melting point of 163-164°C, and molecular formula C29H48O. This compound is known for its significant biological activities, including antibacterial, antimalarial, anti-inflammatory, antioxidant, and anticancer effects. By employing advanced techniques like 1D and 2D NMR spectroscopy, the study provides precise structural elucidation of stigmasterol, contributing to natural product research and reinforcing the medicinal potential of guava leaves as a source of pharmacologically active compounds. This adds to the existing knowledge of the plant’s bioactive components and their applications in medicinal chemistry