Surface sensitive infrared spectroelectrochemistry using palladium electrodeposited on ITO-modified internal reflection elements

Phan, Vi Thuy Thi; Andvaag, Ian R.; Boyle, Nicole D; Flaman, Grace T; Unni, Bipinlal; Burgess, Ian J.

doi:10.1039/d1cp05130j

Cited by 8 publications

(12 citation statements)

References 59 publications

(62 reference statements)

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“…However, relatively thick films of the second metal are required to ensure that the resulting surface is free of pinhole defects, which compromises the optimal SEIRAS activity of the interface. In recent years, we have promoted the use of conductive metal oxides (CMOs) as a base layer for ATR-SEIRAS and reported that such materials are infrared transparent yet conductive, allowing metal nanoparticle films to be directly electrodeposited on thin (∼20 nm) CMO films coated on the surface of an IRE. , Metal on CMO modified IREs was shown to give strong ATR-SEIRAS signals and is far more robust in electrochemical environments compared to metal films directly deposited on IRE surfaces. , …”

Section: Resultsmentioning

confidence: 99%

Oxygen Vacancies Alter Methanol Oxidation Pathways on NiOOH

Phan,

Nguyen,

Wang

et al. 2024

J. Am. Chem. Soc.

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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 Nibased 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 DFTcomputed 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 CH 2 O to CHO. This work thus shows the promising role of defect engineering in promoting the electrocatalytic MOR activity and selectivity.

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Section: Resultsmentioning

confidence: 99%

Oxygen Vacancies Alter Methanol Oxidation Pathways on NiOOH

Phan,

Nguyen,

Wang

et al. 2024

J. Am. Chem. Soc.

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“…Specifically, we incorporate a conductive layer of indium tin oxide (ITO) beneath thin plasmonic Au. This approach has previously been demonstrated for FTIR applications − and more recently for 2D IR. , We choose to use ALD to fabricate the ITO layer due to the atomic level control that it provides via self-limiting growth and its ability to grow high-quality, low-resistivity thin films . By separating the plasmonic material from the bulk conductor of the electrode, we are able to separately optimize each layer.…”

Section: Resultsmentioning

confidence: 99%

Development and Characterization of Electrodes for Surface-Specific Attenuated Total Reflection Two-Dimensional Infrared Spectroelectrochemistry

Bodine,

Rozyyev,

Elam

et al. 2023

J. Phys. Chem. C

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Electrochemical interfaces still have remaining mysteries surrounding the interfacial region of the electrical double layer, despite being prevalent throughout the energy and water remediation industries. The electrical double layer is where many important dynamic processes such as catalysis and electron transfer occur. The goal of this work is to study the electrical double layer with two-dimensional infrared (2D IR) spectroscopy to experimentally access the details of the structural dynamics of this complex environment. However, there are several experimental challenges to applying 2D IR spectroscopy to this application, such as assuring the surface specificity of the spectrum, optimizing the signal strength while minimizing spectral distortions from dispersion and Fano line shapes, and selecting electrode materials that are both sufficiently IR compatible and conductive. Here we will discuss various considerations when designing 2D IR experiments of electrode interfaces utilizing several substrates and experimental configurations and demonstrate a robust method for 2D IR experiments of electrode interfaces under applied potential that combines nonconducting Si ATR wafers with conductive ITO and thin nanostructured films of plasmonically active Au functionalized with 3-mercapto-2-butanone (MCB). We show that layered electrodes on thin Si ATR wafers with MCB are sensitive to applied potential and that the distortions in the linear and 2D IR spectra are heavily dependent on the morphology of the Au surface.

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“…It is interesting that the plasmon peak of ITO can be tuned from ∼5000 to ∼3000 cm –1 via adjusting its dopant level. , The LSPR resonance is closely related to the free electrons produced by introducing a foreign atom of Sn 4+ into the matrix of In 2 O 3 as n-type doping, which can be further explained by the modified Drude model . Due to its tunability in the infrared region, ITO has great potential in the fields of infrared reflection material, − infrared stealth material, − infrared manipulation, − thermal shielding coating, ,− and smart glass. − Although ITO has been widely used for applications concerned with infrared, to the best of our knowledge, the research of ITO’s LSPR and its coupling effect in infrared reflection enhancement is still at large.…”

Section: Introductionmentioning

confidence: 99%

Electrospun ITO/PAN Nanofiber Mat for Infrared Reflection and Thermal Insulation

Xu,

Zhong,

Liu

et al. 2023

ACS Appl. Opt. Mater.

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The heat release of ambient temperature objects (0−100 °C) is often in the form of mid-to far-infrared radiation outward (∼4000 to 200 cm −1 ). In order to maintain warm objects, it is theoretically feasible to construct a kind of flexible material with infrared reflection ability targeting the band of mid-to far-infrared. In this paper, we proposed a type of nanofiber mat with excellent infrared reflection and thermal insulation performance. The ITO nanoclusters were introduced into the polyacrylonitrile (PAN) nanofibers via the electrospinning technique. The performed experimental test proved that the infrared reflection ability of the nanofiber mat can be enhanced because of the increased diameter of nanofiber upon the introduction of the ITO nanocluster as well as the localized surface plasmon resonance (LSPR) effects of ITO nanoclusters in the mid-to far-infrared range. It worth mentioning that the prepared nanofiber mat showed good air-permeability and mechanical properties due to the PAN matrix. Moreover, the performed experiments and numerical simulation analysis also suggested improved infrared reflection performance with respect to the size of aggregated ITO nanoclusters and their LSPR coupling effects in the nanofiber mat. The performed thermal insulation tests also indicated that the electrospun ITO/PAN nanofiber mat is promising for the thermal insulation of ambient temperature objects via IR radiation regulation.

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Surface sensitive infrared spectroelectrochemistry using palladium electrodeposited on ITO-modified internal reflection elements

Abstract: Palladium nanoparticles have been electrodeposited on the surfaces of conductive indium tin oxide (ITO) modified silicon internal reflection elements. The resulting films are shown to be excellent platforms for attenuated...

Cited by 8 publications

References 59 publications

Oxygen Vacancies Alter Methanol Oxidation Pathways on NiOOH

Oxygen Vacancies Alter Methanol Oxidation Pathways on NiOOH

Development and Characterization of Electrodes for Surface-Specific Attenuated Total Reflection Two-Dimensional Infrared Spectroelectrochemistry

Electrospun ITO/PAN Nanofiber Mat for Infrared Reflection and Thermal Insulation

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