Surface-enhanced Infrared Absorption Research Articles

Optimizing CO Coverage on Rough Copper Electrodes: Effect of the Partial Pressure of CO and Electrolyte Anions (pH) on Selectivity toward Ethylene

The conversion of the initial intermediate CO in the electrochemical reduction reaction of CO2 on the surface of oxide-derived Cu electrodes has been investigated as a function of partial pressure and pH, manipulated by the composition of the electrolyte. We show that in inert gas, an increase in partial pressure of CO results in a continuous increase in Faradaic efficiency (FE) for ethylene, at various potentials ranging from −0.7 to −1.1 V versus RHE, with the highest FE of ∼28% obtained using 1 bar CO at −0.8 V. When the partial pressure of CO is increased in a mixture of CO and CO2, an optimum in the ethylene FE was found for the partial pressure of CO in the range from 0.5 bar (at −1.1 V, FE is ∼45%) to 0.8 bar (at −0.9 V, FE is ∼35%). At lower negative potentials (−0.8 to −0.7 V), the presence of CO2 has negligible influence, and similar data to reduction of CO in inert gas were obtained. Variation of the anion in solution (0.1 M concentration) shows that the optimized FE toward ethylene increases from 5.2% in KH2PO4 to 43.2% in KOH. The observed differences in selectivity are attributed to anion buffering capacity and the associated local pH near the surface of the electrode. Using in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), it was determined that the CO coverage increases as a function of increasing pH, confirming that CO coverage and pH correlate. Collectively, the data herein outline the critical role of reactant partial pressures and the significant effect of anion composition (pH) on the surface coverage of CO and concomitant selectivity in electrochemical reduction of CO2 to ethylene.

Surface-Enhanced Raman Scattering and Surface-Enhanced Infrared Absorption by Plasmon Polaritons in Three-Dimensional Nanoparticle Supercrystals.

Surface-enhanced vibrational spectroscopy strongly increases the cross section of Raman scattering and infrared absorption, overcoming the limited sensitivity and resolution of these two powerful analytic tools. While surface-enhanced setups with maximum enhancement have been studied widely in recent years, substrates with reproducible, uniform enhancement have received less attention although they are required in many applications. Here, we show that plasmonic supercrystals are an excellent platform for enhanced spectroscopy because they possess a high density of hotspots in the electric field. We describe the near field inside the supercrystal within the framework of plasmon polaritons that form due to strong light-matter interaction. From the polariton resonances we predict resonances in the far-field enhancement for Raman scattering and infrared absorption. We verify our predictions by measuring the vibrations of polystyrene molecules embedded in supercrystals of gold nanoparticles. The intensity of surface-enhanced Raman scattering is uniform within 10% across the crystal with a peak integrated enhancement of up to 300 and a peak hotspot enhancement of 105. The supercrystal polaritons induce pairs of incoming and outgoing resonances in the enhanced cross section as we demonstrate experimentally by measuring surface-enhanced Raman scattering with multiple laser wavelengths across the polariton resonance. The infrared absorption of polystyrene is likewise enhanced inside the supercrystals with a maximum enhancement of 400%. We show with a coupled oscillator model that the increase originates from the combined effects of hotspot formation and the excitation of standing polariton waves. Our work clearly relates the structural and optical properties of plasmonic supercrystals and shows that such crystals are excellent hosts and substrates for the uniform and predictable enhancement of vibrational spectra.

Monolayer molecular sensing using infrared leaky waveguide mode

Surface-enhanced infrared absorption spectroscopy is attractive for molecular sensing due to its access to chemical bonds with high detection sensitivity. Such a spectroscopic method typically operates on localized resonances in subwavelength structured antennas and metamaterials. In this paper, we demonstrate monolayer octadecanethiol detection by using the leaky guided mode in a metal–insulator–metal waveguide, whose angle-tunable dispersion enables coupling to molecular vibrations with a frequency-variable optical resonance. Our results show that, by changing the incident angle from 15° to 75°, the resonance frequency of the leaky guided mode is scanned around the CH2 vibration modes with frequency detuning from −200 cm−1 to 350 cm−1 in wavenumber. As the frequency detuning increases, the vibration signal of both the CH2 symmetric and asymmetric modes increases first and then decreases. The maximum vibration signal of 1%–1.5% is reached at positive and negative frequency detuning values of ±100 cm−1. These sensing properties are explained with a coupled-oscillator model, which suggests that both enhanced near-field and coupling strength between the optical resonance and molecular vibration play an important role for the optimal sensing performance.

The rational adjusting of proton-feeding by Pt-doped FeP/C hollow nanorod for promoting nitrogen reduction kinetics

Following the guidance of nitrogenase, the natural iron-based catalysts with remarkably high activity in nitrogen reduction reaction (NRR) may be a talent option to develop artificial molecular mimics. However, the electrochemical NRR process of iron-based catalysts still suffers from the high overpotential, poor lifespan, and slow reaction kinetics of the hydrogenation process. Through a controllable etching and in-situ carbonating process, a Pt-doped FeP/C hollow nanorod catalysts was fabricated. Driven by the doped Pt atom, the catalyst solves the key kinetic problem about insufficient proton feeding in the process of nitrogen reduction, and actively transfers protons to intermediates of the hydrogenation steps in NRR. Moreover, the as-prepared catalyst presents the highest NH3 yield value of 10.22 μg h−1 cm−2 among multitudinous Fe based catalysts at lower potential of −0.05 V (vs. RHE) with an excellent Faraday efficiency (FE) of 15.3 %, which is higher than FeP/C without the Pt-driven proton-feeding effect, and the cathodic current density presents no significant change within 50 h. In addition, the density functional theory (DFT) and Attenuated total reflection surface-enhanced infrared absorption spectrum (ATR-SEIRAS) results verify the reaction path and protons-feeding kinetic process.

A novel vibrational spectroscopy using spintronic–plasmonic antennas: Magneto-refractive surface-enhanced infrared absorption

We present experimental and theoretical results of the molecular sensing performance of a novel platform based on magnetic modulation of surface-enhanced infrared absorption spectroscopy. For this, we study the effect that molecular infrared vibrations of a PMMA layer have on the optical and magneto-refractive response of spintronic antennas. Specifically, a periodic array of rods is fabricated from giant-magneto-resistance Au/Ni81Fe19 metallic multilayers, and the effect of depositing a layer of PMMA on top of the array is investigated from both experimental and theoretical points of view. We find that the relative changes induced by the infrared vibrations of PMMA on the magneto-refractive signal are larger than the relative changes induced on the optical transmission. This result indicates that the magneto-refractive response is more sensitive to the excitation of molecular vibrations than the optical response and fosters the development of a novel type of an infrared sensing technique based on spintronic antennas: Magneto-Refractive Surface-Enhanced Infrared Absorption (SEIRA) Spectroscopy.

Cation-Dependent Interfacial Structures and Kinetics for Outer-Sphere Electron-Transfer Reactions

The kinetics of aqueous outer-sphere electron-transfer (ET) reactions are determined in large part by noncovalent electrostatic interactions that originate from the surrounding electrolyte solution. In this work, we examine the role of spectator cations in modifying the rate of heterogeneous ET for an [Fe(CN)6]3–/[Fe(CN)6]4– redox pair. We combine the results of electrochemical measurement, in situ surface-enhanced infrared absorption spectroscopy (SEIRAS), classical molecular dynamics simulation, and theoretical modeling to demonstrate how changing the identity of the spectator cation species over a series that includes Li+, Na+, K+, Rb+ to Cs+ influences the solvation properties and ET kinetics of the redox species. By analyzing the results in the context of the Marcus–Hush–Chidsey (MHC) theory, we find that the solvent reorganization energy increases systematically as the cationic radius decreases. The trend can be attributed to cation-dependent coordination environments of the redox species, whereby more cations of less charge density such as Cs+ than Li+ are present in the redox solvation shell in bulk and at the electrified interface, promoting weaker hydrogen bonds and lowering the effective interfacial static dielectric constant. We discuss the implications of these findings for enabling the tunability of reaction thermodynamics and rates in electrochemical processes.

Impact of membrane protein-lipid interactions on formation of bilayer lipid membranes on SAM-modified gold electrode

In protein film electrochemistry for redox-active membrane proteins, the reconstitution of protein-tethered bilayer lipid membranes (ptBLMs) can maximize their functionality and stability at electrolyte/electrode interfaces. To understand the impact of protein–lipid interactions on the ptBLM formation, we tracked the reconstitution process of a lipid bilayer in the presence or the absence of a transmembrane enzyme of cytochrome c-dependent nitric oxide reductase (cNOR) on a mixed self-assembled monolayer (SAM)/Au electrode. Time-resolved surface-enhanced infrared absorption (SEIRA) spectroscopy and electrochemical measurements revealed that the protein–lipid interaction affected the formation kinetics for the phospholipid bilayer and the electrocatalytic stability of the cNOR-modified electrode but not the fluidity of the phospholipid bilayer.

In Situ Spectroelectrochemical Investigations of Electrode-Confined Electron-Transferring Proteins and Redox Enzymes.

This perspective analyzes recent advances in the spectroelectrochemical investigation of redox proteins and enzymes immobilized on biocompatible or biomimetic electrode surfaces. Specifically, the article highlights new insights obtained by surface-enhanced resonance Raman (SERR), surface-enhanced infrared absorption (SEIRA), protein film infrared electrochemistry (PFIRE), polarization modulation infrared reflection–absorption spectroscopy (PMIRRAS), Förster resonance energy transfer (FRET), X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and differential electrochemical mass spectrometry (DMES)-based spectroelectrochemical methods on the structure, orientation, dynamics, and reaction mechanisms for a variety of immobilized species. This includes small heme and copper electron shuttling proteins, large respiratory complexes, hydrogenases, multicopper oxidases, alcohol dehydrogenases, endonucleases, NO-reductases, and dye decolorizing peroxidases, among other enzymes. Finally, I discuss the challenges and foreseeable future developments toward a better understanding of the functioning of these complex macromolecules and their exploitation in technological devices.

Fluorophosphate-Based Nonflammable Concentrated Electrolytes with a Designed Lithium-Ion-Ordered Structure: Relationship between the Bulk Electrolyte and Electrode Interface Structures.

We propose a molecular design for lithium (Li)-ion-ordered complex structures in nonflammable concentrated electrolytes that facilitates the Li-ion battery (LIB) electrode reaction to produce safer LIBs. The concentrated electrolyte, composed of Li bis(fluorosulfonyl)amide (FSA) salt and a nonflammable tris(2,2,2-trifluoroethyl) phosphate (TFEP) solvent, showed no electrode reaction (i.e., no Li-ion intercalation into the negative graphite electrode); however, introducing a small molecular additive (acetonitrile [AN]) into concentrated TFEP-based electrolytes is shown to improve the battery electrode reaction, leading to reversible charge/discharge behavior. Combined high-energy X-ray total scattering experiments incorporating all-atom molecular dynamics simulations were used to visualize Li-ion complexes at the molecular level and revealed that (1) Li ions form mononuclear complexes in a concentrated LiFSA/TFEP (without additives) owing to solvation steric effects arising from the molecular size of TFEP and (2) adding a small-sized additive, AN, reduces the steric effect and triggers a change in Li-ion structures, i.e., the formation of a specific Li-ion-ordered structure linked via FSA anions. These Li-ion-ordered complexes stabilize the energy of the lowest unoccupied molecular orbital (LUMO) on FSA anions, which is key to producing an anion-derived solid electrolyte interphase (SEI) at the graphite electrode. We performed in situ surface-enhanced infrared absorption spectroscopy and discussed the electrode/electrolyte interface and SEI formation mechanisms in TFEP-based concentrated electrolyte systems.

Confined hydration in nanometer-graded plasma polymer films: Insights from surface-enhanced infrared absorption spectroscopy

To shed light on recently explored long-range surface forces generated by subsurface-confined water, the structural characteristics of water molecules penetrating into nanoporous homogeneous and nanograded siloxane plasma polymer films (PPFs) over the time scale of 24 hours are studied by surface-enhanced IR spectroscopy (SEIRAS). Chemically graded PPFs, with embedded hydrophobic-to-hydrophilic gradient, are found to significantly change the average interfacial water orientation due to a unique nanoporous morphology and silanol group coordination. Diffusion of water through the hydrophobic SiO:CH matrix creates an evolution of the coordination of matrix silanol groups, which are eventually deprotonated as soon as the hydration network connects to the aqueous environment. This occurs after ~6 hours of water immersion and coincides with the change of average interfacial water orientation. Both effects are present on hydrophobic samples, but are significantly amplified by the presence of the subsurface vertical amphiphilic gradient (Vgrad), whereas enhanced water uptake in oxygen-plasma modified graded PPFs is covering such effects.

Efficient Electrocatalytic CO2 Reduction to C2+ Alcohols at Defect-Site-Rich Cu Surface

Summary Electrochemical CO2 reduction is a promising approach for upgrading excessive CO2 into value-added chemicals, while the exquisite control of the catalyst atomic structures to obtain high C2+ alcohol selectivity has remained challenging due to the intrinsically favored ethylene pathways at Cu surface. Herein, we demonstrate a rational strategy to achieve ∼70% faradaic efficiency toward C2+ alcohols. We utilized a CO-rich environment to construct Cu catalysts with stepped sites that enabled high surface coverages of ∗CO intermediates and the bridge-bound ∗CO adsorption, which allowed to trigger CO2 reduction pathways toward the formation alcohols. Using this defect-site-rich Cu catalyst, we achieved C2+ alcohols with partial current densities of > 100 mA·cm−2 in both a flow-cell electrolyzer and a membrane electrode assembly (MEA) electrolyzer. A stable alcohol faradaic efficiency of ∼60% was also obtained, with ∼500 mg C2+ alcohol production per cm2 catalyst during a continuous 30-h operation.

High-sensitivity nanophotonic sensors with passive trapping of analyte molecules in hot spots

Nanophotonic resonators can confine light to deep-subwavelength volumes with highly enhanced near-field intensity and therefore are widely used for surface-enhanced infrared absorption spectroscopy in various molecular sensing applications. The enhanced signal is mainly contributed by molecules in photonic hot spots, which are regions of a nanophotonic structure with high-field intensity. Therefore, delivery of the majority of, if not all, analyte molecules to hot spots is crucial for fully utilizing the sensing capability of an optical sensor. However, for most optical sensors, simple and straightforward methods of introducing an aqueous analyte to the device, such as applying droplets or spin-coating, cannot achieve targeted delivery of analyte molecules to hot spots. Instead, analyte molecules are usually distributed across the entire device surface, so the majority of the molecules do not experience enhanced field intensity. Here, we present a nanophotonic sensor design with passive molecule trapping functionality. When an analyte solution droplet is introduced to the sensor surface and gradually evaporates, the device structure can effectively trap most precipitated analyte molecules in its hot spots, significantly enhancing the sensor spectral response and sensitivity performance. Specifically, our sensors produce a reflection change of a few percentage points in response to trace amounts of the amino-acid proline or glucose precipitate with a picogram-level mass, which is significantly less than the mass of a molecular monolayer covering the same measurement area. The demonstrated strategy for designing optical sensor structures may also be applied to sensing nano-particles such as exosomes, viruses, and quantum dots.

Binding of tyrosine kinase inhibitor to epidermal growth factor receptor: surface-enhanced infrared absorption microscopy reveals subtle protein secondary structure variations.

Surface-Enhanced Infrared Absorption (SEIRA) has been proposed as a valuable tool for protein binding studies, but its performances have been often proven on model proteins undergoing severe secondary structure rearrangements, while ligand binding only marginally involves the protein backbone in the vast majority of the biologically relevant cases. In this study we demonstrate the potential of SEIRA microscopy for highlighting the very subtle secondary structure modifications associated with the binding of Lapatinib, a tyrosine kinase inhibitor (TKI), to epidermal growth factor receptor (EGFR), a well-known driver of tumorigenesis in pathological settings such as lung, breast and brain cancers. By boosting the performances of Mid-IR plasmonic devices based on nanoantennas cross-geometry, accustoming the protein purification protocols, carefully tuning the protein anchoring methodology and optimizing the data analysis, we were able to detect EGFR secondary structure modification associated with few amino acids. A nano-patterned platform with this kind of sensitivity bridges biophysical and structural characterization methods, thus opening new possibilities in studying of proteins of biomedical interest, particularly for drug-screening purposes.

Dispersion-based intertwined SEIRA and SPR effect detection of 2,4-dinitrotoluene using a plasmonic metasurface.

Surface enhanced infrared absorption (SEIRA) spectroscopy and surface plasmon resonance (SPR) make possible, thanks to plasmonics nanoantennas, the detection of low quantities of biological and chemical materials. Here, we investigate the infrared response of 2,4-dinitrotoluene deposited on various arrays of closely arranged metal-insulator-metal (MIM) resonators and experimentally show how the natural dispersion of the complex refractive index leads to an intertwined combination of SEIRA and SPR effect that can be leveraged to identify molecules. They are shown to be efficient for SEIRA spectroscopy and allows detecting of the dispersive explosive material, 2,4-dinitrotoluene. By changing the in-plane parameters, a whole spectral range of absorptions of 2,4-DNT is scanned. These results open the way to the design of sensors based on SEIRA and SPR combined effects, without including a spectrometer.

Understanding the Enhanced Methanol Oxidation Reactivity on Sulfur-Organic Compound Decorated Pt Electrode in Alkaline Media

Due to the rapid increase in environmental and energy issues, it is required to replace fossil fuel-driven conventional internal combustion engines with an energy conversion system using sustainable fuels. Although fuel cell is one of the possible candidates due to its high efficiency, the storage and transportation of hydrogen fuel hinder its widespread use.1 To overcome this problem, hydrogen careers, hydrogen-rich liquid and solid-phase materials, have been proposed as alternative fuels for fuel cell systems. Among the hydrogen carriers, methanol is one of the promising candidates due to its low production cost and high energy density. However, the slow kinetics of the methanol oxidation reaction (MOR), which proceeds via a complex six-electron pathway, limits the overall efficiency of the direct methanol fuel cell (DMFC).2 Much effort has been put into improving the MOR activity, including the development of electrocatalyst by metal alloying and surface modification of the electrocatalyst by thiol derivatives.3 Here, we focused on using sulfur-organic compound copolymer synthesized from S8 and organic molecules as a surface modifier. We then explored the reaction mechanisms on Pt surface in the alkaline environment by tracking the surface-bound intermediates using in situ surface-enhanced infrared absorption spectroscopy (SEIRAS). We selected styrene as an organic component and synthesized sulfur-organic compound copolymer (poly(s-st)). Synthesized poly(s-st) was decorated on the Pt surface by simply immersing the electrode into the poly(s-st)-contained solution. Cyclic voltammogram and X-ray photoelectron spectroscopy confirm the surface modification of the Pt surface by poly(s-st), which was stable after 5 cycles of potential cycling in 0.1 M KOH electrolyte. The oxidation current at 0.78 V vs. RHE, which is related to the MOR, was more significant than the pristine Pt electrode, which confirms the improvement of the MOR activity by poly(s-st) modification. The degree of activity enhancement became more substantial with the increase in alkyl chain length of alcohol fuels (methanol < propanol < 1-butanol), suggesting the reason of the enhanced activity to be the hydrophobic interaction between phenyl group of a surface modifier and alkyl portion of alcohol fuels which could facilitate the fuel supply on Pt electrode. In order to support our hypothesis, we performed SEIRAS measurement, where we observed a peak corresponds to the site-blocking species at ca. 1500 cm-1 for pristine Pt surface, while no corresponding peak was observed for poly(s-st) modified Pt surface. We will discuss the changes in the surface reaction mechanism based on the direct observation of the reaction intermediates by SEIRAS. It will also be demonstrated that the holistic information about the nature of the adsorbed species can provide a strategy to design the surface modifier to tune the energetics of key reaction intermediates, leading to further improvements in electrocatalytic activity for the methanol oxidation reaction.[1] Z-F. Li et al. Electrochim. Acta. 2017, 228, 351–360.[2] C. Lamy et al. J Appl. Electrochem. 2001, 31, 799–809.[3] H. Zimmermann et al. Chem. Eur. J. 2000, 4, 592–599.

Local enhanced site in surface enhanced infrared absorption with gold nano particle array by Rigorous coupled-wave analysis

Surface enhanced infrared absorption (SEIRA) is a phenomenon by which infrared absorption of molecules adsorbed onto metal evaporated films is greatly enhanced. To clarify the enhancement mechanism in the evaporated films, we simulated the distribution of the enhancement field between Au nano-square columns by rigorous coupled wave analysis (RCWA). No maximum enhancement was observed on the particle surface. This result demonstrates that the first layer effect is not dominant for the increase in this system of columns. Furthermore, the enhanced field oscillates periodically between the particles. This periodic oscillation is not plasmon behavior seen in the visible region. Results indicate the existence of enhancement mechanisms other than plasmons and indicate the possibility that the interference effect enhances infrared absorption.

Asp22 drives the protonation state of the Staphylococcus epidermidis glucose/H+ symporter

The Staphylococcus epidermidis glucose/H+ symporter (GlcPSe) is a membrane transporter highly specific for glucose and a homolog of the human glucose transporters (GLUT, SLC2 family). Most GLUTs and their bacterial counterparts differ in the transport mechanism, adopting uniport and sugar/H+ symport, respectively. Unlike other bacterial GLUT homologs (for example, XylE), GlcPSe has a loose H+/sugar coupling. Asp22 is part of the proton-binding site of GlcPSe and crucial for the glucose/H+ co-transport mechanism. To determine how pH variations affect the proton site and the transporter, we performed surface-enhanced IR absorption spectroscopy on the immobilized GlcPSe We found that Asp22 has a pKa of 8.5 ± 0.1, a value consistent with that determined previously for glucose transport, confirming the central role of this residue for the transport mechanism of GlcPSe A neutral replacement of the negatively charged Asp22 led to positive charge displacements over the entire pH range, suggesting that the polarity change of the WT reflects the protonation state of Asp22 We expected that the substitution of the residue Ile105 for a serine, located within hydrogen-bonding distance to Asp22, would change the microenvironment, but the pKa of Asp22 corresponded to that of the WT. A167E mutation, selected in analogy to the XylE, introduced an additional protonatable site and perturbed the protonation state of Asp22, with the latter now exhibiting a pKa of 6.4. These studies confirm that Asp22 is the proton-binding residue in GlcPSe and show that charged residues in its vicinity affect the pKa of glucose/H+ symport.

Micro- and Nanoscale Spectroscopic Investigations of Threonine Influence on the Corrosion Process of the Modified Fe Surface by Cu Nanoparticles.

The work presents a comprehensive vibrational analysis of the process of adsorption of threonine (Thr) onto an Fe surface with deposited Cu nanoparticles (NPs) (of about 4–5 nm in size) in a corrosive environment. The application of surface-enhanced Raman spectroscopy (SERS) and surface-enhanced infrared absorption spectroscopy (SEIRA) provides the opportunity for detailed description of adsorption geometry of amino acid onto a metal surface. The combination of conventional infrared spectroscopy (IR) with atomic force microscopy (AFM) resulted in a nano-SEIRA technique which made it possible to provide a precise description of adsorbate binding to the metal surface. The studies presented confirmed that there is a very good correlation between the spectra recorded by the SERS, SEIRA, and nano-SEIRA techniques. Threonine significantly influenced the process of corrosion of the investigated surface due to the existing strong interaction between the protonated amine and carboxylate groups and the CuNPs deposited onto the Fe surface. In addition, the application of two polarization modulations (s and p) in nano-SEIRA allows subtle changes to be observed in the molecule geometry upon adsorption, with the carboxylate group of Thr being almost horizontally oriented onto the metal surface; whereas the amine group that contains nitrogen is oriented perpendicular to this surface.

Origin of a High Overpotential of Co Electrodeposition in a Room-Temperature Ionic Liquid.

Metal electrodeposition in room-temperature ionic liquids (RTILs) often shows high overpotentials. Although this is often explained by the formation of a negatively charged metal complex due to the coordination of RTIL anions and the hindrance of its close approach onto the negatively charged electrode, we propose an alternative model based upon surface-enhanced infrared absorption spectroscopy measurements under Co electrodeposition. We found that the anionic first layer exists on the negatively charged electrode, and its replacement with a cationic one and Co electrodeposition both begin at an identical onset potential. The correlation between the interfacial structure and the electrodeposition reaction that can be modified by additives indicated that the high overpotential can be mainly attributed to the restructuring of the characteristic interfacial multilayer structure stabilized by its charge order, which is required for the reorganization of solvent ions after the reduction of Co2+.

Sol–Gel and Electrospinning Synthesis of Silica–Hydroxyapatite–Silver Nanofibers for SEIRAS and SERS

Surface-enhanced Raman spectroscopy (SERS) and Surface-enhanced infrared absorption spectroscopy (SEIRAS) are both novel techniques favored by the excitation of surface plasmons onto metal nanostructures. The light emitted from the metal surface couples with the vibrational transitions of molecules in proximity, enhancing its spectral response and leading to more sensitive and effective spectroscopic analysis. The absence of inexpensive and reproducible substrates is among the major impediments to the accurate implementation and optimal performance of the technique. The development of a low-cost active substrate based on silica–hydroxyapatite through sol–gel synthesis and electrospinning is addressed in the present study. Fibers of 512 ± 199 nm diameter were produced after sintering at 1150 °C on the electrospun mats. The fibers are fixed to an indium tin oxide (ITO) glass base for electrodeposition with 10 and 20 mM AgNO3 at 1.5 and 3.3 V at different time periods. Electrodeposition produced silver nanorods and nanocubes on the fibers. The SERS and SEIRAS activity of each one of the nine supports was tested using pyridine 1 nM, comparing it with the spectrum of pyridine 1 mM. An enhancement factor of 2.01 × 106 for the band at 3335 cm−1 was obtained during a SEIRAS essay for the support doped for 2 min at 3.3 V with 10 mM silver nitrate solution. The highest SERS enhancement factor was 3.46 × 108, for the band at 1567 cm−1 in the substrate doped for 5 min at 1.5 V with silver nitrate solution at 10 mM. After testing both samples with 10−4 M violet crystal solution, no SERS enhancement factor was found, but higher band resolution in the spectra was observed.