Surface-enhanced Infrared Absorption Research Articles

Applications of metals and metal compounds in improving the sensitivity of microfluidic biosensors - a review.

The enhancement of detection sensitivity in microfluidic sensors has been a continuously explored field. Initially, many strategies for sensitivity improvement involved introducing enzyme cascade reactions, but enzyme-based reactions posed challenges in terms of cost, stability, and storage. Therefore, there is an urgent need to explore enzyme-free cascade amplification methods, which are crucial for expanding the application range and improving detection stability. Metal or metal compound nanomaterials have gained great attention in the exploitation of microfluidic sensors due to their ease of preparation, storage, and lower cost. The unique physical properties of metallic nanomaterials, including surface plasmon resonance, surface-enhanced Raman scattering, metal-enhanced fluorescence, and surface-enhanced infrared absorption, contribute significantly to enhancing detection capabilities. The metal-based catalytic nanomaterials, exemplified by Fe3O4 nanoparticles and metal-organic frameworks, are considered viable alternatives to biological enzymes due to their excellent performance. Herein, we provide a detailed overview of the applications of metals and metal compounds in improving the sensitivity of microfluidic biosensors. This review not only highlights the current developments but also critically analyzes the challenges encountered in this field. Furthermore, it outlines potential directions for future research, contributing to the ongoing development of microfluidic biosensors with improved detection sensitivity.

Enhancing Electrocatalytic CO2-to-CO Conversion by Weakening CO Binding through Nitrogen Integration in the Metallic Fe Catalyst.

Metallic iron (Fe) typically demonstrates the unfavorable catalytic activity for the CO2 reduction reaction (CO2RR), mainly attributed to the excessively strong binding of CO products on Fe sites. Toward this end, we employed an effective approach involving electronic structure modulation through nitrogen (N) integration to enhance the performance of the CO2RR. Here, an efficient catalyst has been developed, composed of N-doped metallic iron (Fe) nanoparticles encapsulated in a porous N-doped carbon framework. Notably, this N-integrated Fe catalyst displays significantly enhanced performance in the electrocatalytic reduction of CO2, yielding the highest CO Faradaic efficiency of 97.5% with a current density of 6.68 mA cm-2 at -0.7 V versus the reversible hydrogen electrode. The theoretical calculations, combined with the in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy study, reveal that N integration modulates the electron density around Fe, resulting in the weakening of the binding strength between the Fe active sites and *CO intermediates, consequently promoting the desorption of CO and the overall CO2RR process.

Cation Dependence of Enniatin B/Membrane-Interactions Assessed Using Surface-Enhanced Infrared Absorption (SEIRA) Spectroscopy.

Enniatins are mycotoxins with well-known antibacterial, antifungal, antihelmintic and antiviral activity, which have recently come to attention as potential mitochondriotoxic anticancer agents. The cytotoxicity of enniatins is traced back to ionophoric properties, in which the cyclodepsipeptidic structure results in enniatin:cation-complexes of various stoichiometries proposed as membrane-active species. In this work, we employed a combination of surface-enhanced infrared absorption (SEIRA) spectroscopy, tethered bilayer lipid membranes (tBLMs) and density functional theory (DFT)-based computational spectroscopy to monitor the cation-dependence (Mz+=Na+, K+, Cs+, Li+, Mg2+, Ca2+) on the mechanism of enniatin B (EB) incorporation into membranes and identify the functionally relevant EBn : Mz+ complexes formed. We find that Na+ promotes a cooperative incorporation, modelled via an autocatalytic mechanism and mediated by a distorted 2 : 1-EB2 : Na+ complex. K+ (and Cs+) leads to a direct but less efficient insertion into membranes due to the adoption of "ideal" EB2 : K+ sandwich complexes. In contrast, the presence of Li+, Mg2+, and Ca2+ causes a (partial) extraction of EB from the membrane via the formation of "belted" 1 : 1-EB : Mz+ complexes, which screen the cationic charge less efficiently. Our results point to a relevance of the cation dependence for the transport into the malignant cells where the mitochondriotoxic anticancer activity is exerted.

Tailoring the catalytic microenvironment of CuO with hydrophobic CuSA2 for selective CO2 electroreduction to C2+ products

Advancing the Faraday efficiency (FE) and current density of Cu catalyzed electrochemical CO2 reduction (ECR) reaction to produce C2+ products is important for its practical applications. Constructing a hydrophobic interface to regulate the local reaction environment is an effective method to improve the selectivity of C2+ products, but it is limited by the low reaction current density. In this work, we fabricated a novel hydrophobic and ECR active copper stearate (CuSA2) decorated CuO nanoparticle catalyst (CuO/CuSA2) for ECR reaction toward C2+ products. As a result, the CuO/CuSA2 catalyst achieved an FE of 61.33 % and a partial current density of 429.33 mA cm−2 for C2+ products. The CuSA2 and CuO nanoparticle cooperate very well for the formation of C2+ products. The in-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and electrochemical adsorption experiments indicated that the hydrophobic CuSA2 regulated the local ECR reaction environment. The local ∗CO2.- and *CO adsorption were strengthened by hydrophobic CuSA2 modification while the H2O adsorption was inhibited. CuO nanoparticle promotes *CO coupling reaction and enhances C2 intermediates (*OCCOH and *OC2H5) adsorption. Hydrophobic CuSA2 and CuO nanoparticle synergistically promote the generation of C2+ products. This work provides new insights into the design of hydrophobic CO2 reduction electrocatalysts for the preparation of C2+ products.

Molecular tuning boosts asymmetric C-C coupling for CO conversion to acetate.

Electrochemical carbon dioxide/carbon monoxide reduction reaction offers a promising route to synthesize fuels and value-added chemicals, unfortunately their activities and selectivities remain unsatisfactory. Here, we present a general surface molecular tuning strategy by modifying Cu2O with a molecular pyridine-derivative. The surface modified Cu2O nanocubes by 4-mercaptopyridine display a high Faradaic efficiency of greater than 60% in electrochemical carbon monoxide reduction reaction to acetate with a current density as large as 380 mA/cm2 in a liquid electrolyte flow cell. In-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy reveals stronger *CO signal with bridge configuration and stronger *OCCHO signal over modified Cu2O nanocubes by 4-mercaptopyridine than unmodified Cu2O nanocubes during electrochemical CO reduction. Density function theory calculations disclose that local molecular tuning can effectively regulate the electronic structure of copper catalyst, enhancing *CO and *CHO intermediates adsorption by the stabilization effect through hydrogen bonding, which can greatly promote asymmetric *CO-*CHO coupling in electrochemical carbon monoxide reduction reaction.

Enhanced Electrochemical CO2 Reduction to Formate over Phosphate-Modified In: Water Activation and Active Site Tuning.

Electrochemical CO2 reduction reaction (CO2RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish CO2 activation and slow water dissociation. In this work, we construct a (P-O)δ- modified In catalyst that exhibits high activity and selectivity in electrochemical CO2 reduction to formate. A combination of in-situ characterizations and kinetic analyses indicate that (P-O)δ- has a strong interaction with K+(H2O)n, which effectively accelerates water dissociation to provide protons. In-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) measurements together with density functional theory (DFT) calculations disclose that (P-O)δ- modification leads to a higher valence state of In active site, thus promoting CO2 activation and HCOO* formation, while inhibiting competitive hydrogen evolution reaction (HER). As a result, the (P-O)δ- modified oxide-derived In catalyst exhibits excellent formate selectivity across a broad potential window with a formate Faradaic efficiency as high as 92.1% at a partial current density of ~200 mA cm-2 and a cathodic potential of -1.2 V vs. RHE in an alkaline electrolyte.

Revealing the Regulation Effect of Surface Charge at Aromatic Interface to Dynamic Conformational Changes of α‐Synuclein at Early Aggregation Stage

Comprehensive SummaryThe aggregation of α‐synuclein (α‐syn) is strongly influenced by membrane interfaces, but the mechanism of transition from monomers to oligomers at early aggregation stage is not clear. Here, we investigate the adsorption and structure changes of α‐syn on oppositely charged aromatic interfaces through in‐situ surface‐enhanced infrared absorption (SEIRA) spectroscopy and nano‐IR technique. The results show that the synergy of electrostatic and hydrophobic interactions leads to a “fast‐slow” two‐step aggregation pathway on negatively charged interface. Surface adsorption induces the formation of an extended helix structure and subsequently partial helix unwinding in NAC region, which enables the hydrophobic stacking between nearby NAC regions. Stable antiparallel β‐sheet rich aggregates are gradually emerging as further interactions of monomers with the fast formed “first layer”. Monomers electrostatically adsorb on positively charged interface by C‐terminus with NAC region and N‐terminus stretched in solvent, which serve as an aggregation core and induce further adsorption and gradual formation of aggregates with C‐terminus exposure. Our results demonstrate the modulation of surface charge and synergy of electrostatic and hydrophobic interactions on the interaction modes and aggregation pathways, which provide insights into dynamic conformation changes of α‐syn at early aggregation stage and imply the important role of spatial‐temporal heterogeneity of membranes in α‐synucleinopathies.

Gradient High-Q Dielectric Metasurfaces for Broadband Sensing and Control of Vibrational Light-Matter Coupling.

Surface-enhanced infrared absorption spectroscopy (SEIRA) has emerged as a powerful technique for ultrasensitive chemical-specific analysis. SEIRA can be realized by employing metasurfaces that can enhance light-matter interactions in the spectral bands of molecular vibrations. Increasing sample complexity emphasizes the need for metasurfaces that can operate simultaneously at different spectral bands, both accessing rich spectral information over a broad band, and resolving subtle differences in the absorption fingerprints through narrow-band resonances. Here, a novel concept of resonance-gradient metasurfaces is introduced, where the required spectral selectivity is achieved via local high-quality-factor (high-Q) resonances, while the continuous coverage of a broad band is enabled by the gradual adjustment of the unit-cell dimensions along the planar structure. The highly tailorable design of the gradient metasurfaces provides flexibility for shaping the spectral sampling density to match the relevant bands of target analytes while keeping a compact device footprint. The versatility of the gradient metasurfaces is demonstrated through several sensing scenarios, including polymer mixture deconvolution, detecting a multistep bioassay, and identification of the onset of vibrational strong coupling regime. The proposed gradient-resonance platform significantly contributes to the rapidly evolving landscape of nonlocal metasurfaces, enabling applications in molecular detection and analysis of fundamental light-matter interaction phenomena.

Modulating surface microenvironment based on Ag-adorned CuO flower-liked nanospheres for strengthening C-‍C coupling during CO2RR

Modulating the surface microenvironment is crucial in strengthening CC coupling, leading to increasing selectivity in the production of multi-carbon (C2+) products during CO2 electroreduction. Herein, we have concentrated on investigating how to control the effect of surface distribution of active components of a series of Ag-decorated CuO, denoted as xAg/yCuO. These catalysts with similar chemical elements and morphology are designed, but they exhibit different selectivity in the CO2 electroreduction process. As a result, the Ag particles in 3Ag/CuO aggregates, while the Ag in 2Ag/2CuO and Ag/3CuO is uniformly distributed on the flower-like CuO nanosphere. Besides, 3Ag/CuO has the highest Faraday efficiency (FE) of CO with a value of 30.9 % at 0.8 V vs. RHE, demonstrating rich-Ag catalysts are beneficial to produce CO. 2Ag/2CuO shows excellent FEC2H4 of 51.4 % at -1.2 V vs. RHE due to the highly dispersed distribution of Ag on the flower-like CuO and higher vacancy O. Ag/3CuO exhibits higher FEH2 compared to other catalysts across a wide potential range, and its minimal impedance is attributed to its exceptional performance in the hydrogen evolution reaction. The proposed reaction pathway for the most effective catalysts 2Ag/2CuO, as determined by in-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), involves the following steps: CO2 →*CO2−→ *COOH → *CO→ *CHO→ *OCHCHO→ *OCHCH2→ C2H4. These findings demonstrate that controlling the surface structure can influence the local environment to enhance the efficiency of CO2 electroreduction.

Role of Electrolyte pH on Water Oxidation for Iridium Oxides.

Understanding the effect of noncovalent interactions of intermediates at the polarized catalyst-electrolyte interface on water oxidation kinetics is key for designing more active and stable electrocatalysts. Here, we combine operando optical spectroscopy, X-ray absorption spectroscopy (XAS), and surface-enhanced infrared absorption spectroscopy (SEIRAS) to probe the effect of noncovalent interactions on the oxygen evolution reaction (OER) activity of IrOx in acidic and alkaline electrolytes. Our results suggest that the active species for the OER (Ir4.x+-*O) binds much stronger in alkaline compared with acid at low coverage, while the repulsive interactions between these species are higher in alkaline electrolytes. These differences are attributed to the larger fraction of water within the cation hydration shell at the interface in alkaline electrolytes compared to acidic electrolytes, which can stabilize oxygenated intermediates and facilitate long-range interactions between them. Quantitative analysis of the state energetics shows that although the *O intermediates bind more strongly than optimal in alkaline electrolytes, the larger repulsive interaction between them results in a significant weakening of *O binding with increasing coverage, leading to similar energetics of active states in acid and alkaline at OER-relevant potentials. By directly probing the electrochemical interface with complementary spectroscopic techniques, our work goes beyond conventional computational descriptors of the OER activity to explain the experimentally observed OER kinetics of IrOx in acidic and alkaline electrolytes.

Novel water/oxygen cycle reaction photo fuel cell for solar conversion and pollutant detection: Based on selective 2-electron collaborative catalysis process

New typed photovoltaic devices, represented by water/oxygen cycle based photo fuel cells (PFCs) as a promising strategy to resolve the fossil energy crisis, have attracted extensive attention for the ideal photo energy conversion and utilization efficiency, spontaneous operation, and miniaturized devices. However, they still have limitations such as low oxygen reduction efficiency and poor stability caused by the complex structure of the cathode. In this work, a synergetic and fast 2-electron water/oxygen cycle reaction based dual-photoelectrode fuel cell (DPFC) is constructed with molecularly imprinted (MI)-CdS/ZnO nanorods (NRs) as photoanode and p-type organic semiconductor polythiophene (pTTh) as photocathode for the first time. The larger self-bias and simple structure endow the device higher open circuit potential (EOCV = 1.07 ± 0.08 V) and ideal output power density (Pmax = 60.5 ± 2.1 μW·cm−2). Attributed to the synergistic reaction effects, the 2-electron water/oxygen cycle is realized by the photocathode-generated H2O2 to serve as shuttle molecule, with outstanding cyclic stability (96 %) in 64 h continuous irradiation. Moreover, a portable self-powered sensor for the typical environmental pollutant atrazine is successfully developed based on this DPFC. A very wide concentration range (0.002 to 50 nM) and a super low detection limit (0.19 pM) is achived via a digital multimeter without the assistance of any signal amplifier. The mechanism, pathway, and active site of the selective reduction process are studied by the attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS). This work has proposed a cheap and regulatable new way to convert and utilize solar energy and provided theoretical guidance for achieving economic power generation and the sensing strategy of self-powered sensors.

Surface Enhanced Infrared Absorption Using Single Conducting Polymer Antennas.

Infrared absorption provides the intrinsic vibrational information on chemical bonds, which is important for identifying molecular moieties. To enhance the sensitivity of infrared absorption, plasmonic antennas have been widely used to localize and concentrate mid-infrared light into nanometer-scale hotspots at desired wavelengths. Here, instead of inorganic plasmonic antennas, we have demonstrated surface-enhanced infrared absorption (SEIRA) using single plasmonic antennas based on a conducting polymer. With commercially available PEDOT:PSS (poly(ethylenedioxythiophene):poly(styrenesulfonate)), the organic plasmonic antennas are in the fashion of single PEDOT:PSS micropillars. The plasmonic resonance of single PEDOT:PSS micropillar antennas can be easily tuned by the micropillar diameter or by the interantenna gap across the mid-infrared frequencies. These organic plasmonic antennas show the ability to enhance the molecular vibrations of CBP (4,4'-bis(N-carbazolyl)-1,1'-biphenyl) molecules with a thickness of about 50 nm, illustrating the good SEIRA sensitivity (with SEIRA sensitivity up to ∼7800) at the single antenna level. Our findings provide another material choice for mid-infrared plasmonic antennas toward SEIRA applications.

Oxygen Vacancies Alter Methanol Oxidation Pathways on NiOOH.

A thorough comprehension of the mechanism underlying the methanol oxidation reaction (MOR) on Ni-based catalysts is critical for future electrocatalytic design and development. However, the mechanism of MOR on these materials remains a matter of controversy. Herein, we combine in situ surface-enhanced infrared absorption spectroscopy (SEIRAS) and density functional theory (DFT) calculations to identify the active sites and determine the mechanism of MOR on monometallic Ni-based catalysts in alkaline media. The SEIRAS results show that formate and (bi)carbonate are formed after the commencement of the MOR with potential-dependent relative distributions. These spectroscopic results are in good agreement with the DFT-computed reaction profiles over an oxygen vacancy, suggesting that the MOR mainly proceeds through the formate-involving pathway, in which the early consumption of methanol yields formate as the major product, while increasing potential drives further oxidation of formate to (bi)carbonate. We also find a parallel pathway for the generation of (bi)carbonate at high potentials that bypasses the formation of formate. The two main pathways are thermodynamically more feasible than the one predominantly reported in the literature for MOR on NiOOH that involves CHO and/or CO as key intermediates. These DFT results are supported by spectroscopic evidence showing that no band associated with CHO or CO can be detected by SEIRAS, which is attributed to the nature of the oxygen vacancies as the active sites, suppressing deep dehydrogenation of CH2O to CHO. This work thus shows the promising role of defect engineering in promoting the electrocatalytic MOR activity and selectivity.

Multi-band Metasurface-Driven Surface-Enhanced Infrared Absorption Spectroscopy for Improved Characterization of in-Situ Electrochemical Reactions.

Surface-enhanced spectroscopy techniques are the method-of-choice to characterize adsorbed intermediates occurring during electrochemical reactions, which are crucial in realizing a green and sustainable future. Characterizing species with low coverage or short lifetimes has so far been limited by low signal enhancement. Recently, single-band metasurface-driven surface-enhanced infrared absorption spectroscopy (SEIRAS) has been pioneered as a promising technology to monitor a single vibrational mode during electrochemical CO oxidation. However, electrochemical reactions are complex, and their understanding requires the simultaneous monitoring of multiple adsorbed species in situ, hampering the adoption of nanostructured electrodes in spectro-electrochemistry. Here, we develop a multi-band nanophotonic-electrochemical platform that simultaneously monitors in situ multiple adsorbed species emerging during cyclic voltammetry scans by leveraging the high resolution offered by the reproducible nanostructuring of the working electrode. Specifically, we studied the electrochemical reduction of CO2 on a Pt surface and used two separately tuned metasurface arrays to monitor two adsorption configurations of CO with vibrational bands at ∼2030 and ∼1840 cm-1. Our platform provides a ∼40-fold enhancement in the detection of characteristic absorption signals compared to conventional broadband electrochemically roughened platinum films. A straightforward methodology is outlined starting with baselining our system in a CO-saturated environment and clearly detecting both configurations of adsorption. In contrast, during the electrochemical reduction of CO2 on platinum in K2CO3, CO adsorbed in a bridged configuration could not be detected. We anticipate that our technology will guide researchers in developing similar sensing platforms to simultaneously detect multiple challenging intermediates, with low surface coverage or short lifetimes.

Mechanistic insights into C-C coupling in electrochemical CO reduction using gold superlattices

Developing in situ/operando spectroscopic techniques with high sensitivity and reproducibility is of great importance for mechanistic investigations of surface-mediated electrochemical reactions. Herein, we report the fabrication of highly ordered rhombic gold nanocube superlattices (GNSs) as substrates for surface-enhanced infrared absorption spectroscopy (SEIRAS) with significantly enhanced SEIRA effect, which can be controlled by manipulating the randomness of GNSs. Finite difference time domain simulations reveal that the electromagnetic effect accounts for the significantly improved spectroscopic vibrations on the GNSs. In situ SEIRAS results show that the vibrations of CO on the Cu2O surfaces have been enhanced by 2.4 ± 0.5 and 18.0 ± 1.3 times using GNSs as substrates compared to those on traditional chemically deposited gold films in acidic and neutral electrolytes, respectively. Combined with isotopic labeling experiments, the reaction mechanisms for C-C coupling of CO electroreduction on Cu-based catalysts are revealed using the GNSs substrates.

Nanostructured Black Silicon as a Stable and Surface-Sensitive Platform for Time-Resolved In Situ Electrochemical Infrared Absorption Spectroscopy.

Attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) is a powerful method for probing interfacial chemical processes. However, SEIRAS-active nanostructured metallic thin films for the in situ analysis of electrochemical phenomena are often unstable under biased aqueous conditions. In this work, we present a surface-enhancing structure based on etched black Si internal reflection elements with Au-coatings for in situ electrochemical ATR-SEIRAS. Using electrochemical potential-dependent adsorption and desorption of 4-methoxypyridine on Au, we demonstrate that black Si-based substrates offer advantages over commonly used structures, such as electroless-deposited Au on Si and electrodeposited Au on ITO-coated Si, due to the combination of high stability, sensitivity, and conductivity. These characteristics are especially valuable for time-resolved measurements where stable substrates are required over extended times. Furthermore, the low sheet resistance of Au layers on black Si reduces the RC time constant of the electrochemical cell, enabling a significantly higher time resolution compared to that of traditional substrates. Thus, we employ black Si-based substrates in conjunction with rapid- and step-scan Fourier transform infrared (FTIR) spectroscopy to investigate the adsorption and desorption kinetics of 4-methoxypyridine during in situ electrochemical potential steps. Adsorption is shown to be diffusion-limited, which allows for the determination of the mean molecular area in a fully established monolayer. Moreover, no significant changes in the peak ratios of vibrational modes with different orientations relative to the molecular axis are observed, suggesting a single adsorption mode and no alteration of the average molecular orientation during the adsorption process. Overall, this study highlights the enhanced performance of black Si-based substrates for both steady-state and time-resolved in situ electrochemical ATR-SEIRAS, providing a powerful platform for kinetic and mechanistic investigations of electrochemical interfaces.

Kinetics Conditioning of (Electro) Chemically Stable Zn Anode with pH Regulation Toward Long-Life Zn-Storage Devices.

The safety, low cost, and high power density of aqueous Zn-based devices (AZDs) appeal to large-scale energy storage. Yet, the presence of hydrogen evolution reaction (HER) and chemical corrosion in the AZDs leads to local OH- concentration increasement and the formation of Znx SOy (OH)z •nH2 O (ZHS) by-products at the Zn/electrolyte interface, causing instability and irreversibility of the Zn-anodes. Here, a strategy is proposed to regulate OH- by introducing a bio-sourced/renewable polypeptide (ɛ-PL) as a pH regulator in electrolyte. The consumption of OH- species is evaluated through in vitro titration and cell in vivo in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy at a macroscopic and molecular level. The introduction of ɛ-PL is found to significantly suppress the formation of ZHS and associated side reactions, and reduce the local coordinated H2 O of the Zn2+ solvation shell, widening electrochemical stable window and suppressing OH- generation during HER. As a result, the inclusion of ɛ-PL improves the cycle time of Zn/Zn symmetrical cells from 15 to 225h and enhances the cycle time of aqueous Zn- I2 cells to 1650h compared to those with pristine electrolytes. This work highlights the potential of kinetical OH- regulation for by-product and dendrite-free AZDs.

Effective free-standing electrodes with refined structure via sputtering Ti sublayer and altering working pressure for electrocatalytic benzaldehyde hydrogenation

Highly effective free-standing electrocatalysts are demanded to reduce biomass-oriented aldehydes to alcohols. Magnetron sputtering is efficient to produce film-based catalysts, but depositing transition metals on carbon fiber paper (CFP) faces the challenge of weak adhesion. Here we introduced a strategy with sputtered Ti as a sublayer to enhance the adhesion between Ni and CFP, and systematically studied the changes in morphology and catalytic performances. Different from the dense structure of Ni directly sputtered on CFP, the Ni on Ti sublayer demonstrates a column-channel architecture, and shows fast electron/ion transfer and stable structure during the reaction. Moreover, the microstructure of Ni film was further modified by regulating the working pressure during sputtering. The enhanced electrocatalytic performance with Ti sublayer is ascribed to the higher adhesion strength, the faster electron/ion transfer and the enriched local concentration of hydronium ions, which are confirmed by electrochemical impedance spectroscopy and in-situ surface-enhanced infrared absorption spectroscopy.

In Situ Infrared Spectroscopic Evidence of Enhanced Electrochemical CO2 Reduction and C-C Coupling on Oxide-Derived Copper.

The reaction mechanism of CO2 electroreduction on oxide-derived copper has not yet been unraveled even though high C2+ Faradaic efficiencies are commonly observed on these surfaces. In this study, we aim to explore the effects of copper anodization on the adsorption of various CO2RR intermediates using in situ surface-enhanced infrared absorption spectroscopy (SEIRAS) on metallic and mildly anodized copper thin films. The in situ SEIRAS results show that the preoxidation process can significantly improve the overall CO2 reduction activity by (1) enhancing CO2 activation, (2) increasing CO uptake, and (3) promoting C-C coupling. First, the strong *COO- redshift indicates that the preoxidation process significantly enhances the first elementary step of CO2 adsorption and activation. The rapid uptake of adsorbed *COatop also illustrates how a high *CO coverage can be achieved in oxide-derived copper electrocatalysts. Finally, for the first time, we observed the formation of the *COCHO dimer on the anodized copper thin film. Using DFT calculations, we show how the presence of subsurface oxygen within the Cu lattice can improve the thermodynamics of C2 product formation via the coupling of adsorbed *CO and *CHO intermediates. This study advances our understanding of the role of surface and subsurface conditions in improving the catalytic reaction kinetics and product selectivity of CO2 reduction.

Synthesized complex-frequency excitation for ultrasensitive molecular sensing

Sensors have emerged as indispensable analytical tools across a wide range of important fields, encompassing environmental monitoring, food safety, and public health. They facilitate early disease diagnosis, personalized medicine, and rapid detection of toxic agents. However, detecting trace molecules remains a significant challenge. Surface-enhanced infrared absorption (SEIRA) based on plasmonic nanostructures, particularly graphene, has emerged as a promising approach to enhance sensing sensitivity. While graphene-based SEIRA offers advantages such as high sensitivity and active tunability, intrinsic molecular damping weakens the interaction between vibrational modes and plasmons. Here, we demonstrate ultrahigh-sensitive molecular sensing based on synthesized complex-frequency waves (CFW). Our experiment shows that CFW can amplify the molecular signals (silk protein monolayer) detected by graphene-based sensor by at least an order of magnitude and can be universally applied to molecular sensing in different phases. Our approach is highly scalable and can facilitate the investigation of light-matter interactions, enabling diverse potential applications in fields such as optical spectroscopy, biomedicine and pharmaceutics.