Robust electrografted interfaces on metal oxides for electrocatalysis – an <i>in situ</i> spectroelectrochemical study

Harris, Tomos G. A. A.; Götz, Robert; Wrzolek, Pierre; Davis, V. A.; Knapp, Caroline E.; Ly, Khoa H.; Hildebrandt, Peter; Schwalbe, Matthias; Weidinger, Inez M.; Zebger, Ingo; Fischer, Anna

doi:10.1039/c8ta02983k

Cited by 37 publications

(46 citation statements)

References 82 publications

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“…3) Imidazole ligands were electrochemically grafted onto the AgNP surface after loading onto the CP electrode, using diazonium starting materials and cyclic voltammetry, according to established protocols. 38 4) PVP-coated AgNPs were commercially purchased and were slightly larger, ~50 nm in diameter ( Fig. 2c).…”

Section: )mentioning

confidence: 99%

Surface Chemistry Modulates CO2 Reduction Reaction Intermediates on Silver Nanoparticle Electrocatalysts

Harris¹,

Chartrand²,

Heidary³

et al. 2020

Preprint

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<div>Electrocatalytic reduction of carbon dioxide (CO2R) to fuels and chemicals is a pressing scientific</div><div>and engineering challenge that is, in part, hampered by a lack of understanding of the surface reaction</div><div>mechanism, even for relatively simple systems. While many efforts have been dedicated to promoting CO2R</div><div>on catalytic surfaces by tuning composition, morphology, and defects, the role of the reaction environment</div><div>around the active site, and how this can be leveraged to modulate CO2R, is less clear. To this end, we</div><div>focused on a model CO2R catalyst, Ag nanoparticles, and carried out a combined electrocatalytic and</div><div>operando Raman spectroscopic investigation of CO2R on their surfaces. Bare Ag and chemically modified</div><div>Ag nanoparticles were investigated to understand how the surface reaction environment dictates</div><div>intermediate binding and catalytic efficiency en route to CO generation. The results revealed that the</div><div>primary product on Ag is CO, which is formed through a doubly-bound CObridge configuration. In contrast,</div><div>electrografted imidazole and polyvinylpyrrolidone (PVP)-coated Ag feature CO in a singly-bound COatop</div><div>configuration on their surfaces, whereas porous zeolitic-imidazolate framework-coated Ag was observed</div><div>to bind both CObridge and COatop. Further, another function of the Ag surface modifications is to dictate the</div><div>type of Ag surface sites which form Ag-C bonds with CO2R intermediates. Through analysis of the of</div><div>electrochemical and spectroscopic data, we deduce which key aspects of CO2R on Ag surface render a</div><div>CO2R system efficient and show how surface chemistry dictates diverging CO2R surface reaction</div><div>mechanisms. The insights gained here are important as they provide the community with a greater</div><div>understanding of heterogeneous CO2R and can be further translated to a number of catalytic systems. </div>

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Section: )mentioning

confidence: 99%

Surface Chemistry Modulates CO2 Reduction Reaction Intermediates on Silver Nanoparticle Electrocatalysts

Harris¹,

Chartrand²,

Heidary³

et al. 2020

Preprint

Self Cite

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“…Alternative functionalization strategies that result in highly stable interfaces include the photochemical grafting of alkenes on oxides surfaces such as ITO (Li and Zuilhof 2012), SnO 2 (Benson et al 2011) and TiO 2 (Franking et al 2009), as well as the electrochemical grafting of diazonium salts (Pinson and Podvorica 2005). Methods for suppressing often-observed multilayer formation during electrografting have been developed, and fast ICT can be achieved, possibly due to improved electronic coupling or the conjugated nature of the interface (Harris et al 2018b). Indeed, the layer-by-layer growth of electrochemically addressable MFM-186 and MFM-180 MOF films was recently demonstrated on both ITO and carbon paper with -COOH terminated interfaces created through the electrografting of diazonium salts (Mitra et al 2018).…”

Section: Mof and Cof Interfaces And Electrochemistrymentioning

confidence: 99%

Artificial photosynthesis with metal and covalent organic frameworks (MOFs and COFs): challenges and prospects in fuel‐forming electrocatalysis

Heidary

Harris

et al. 2019

Physiologia Plantarum

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Mimicking photosynthesis in generating chemical fuels from sunlight is a promising strategy to alleviate society's demand for fossil fuels. However, this approach involves a number of challenges that must be overcome before this concept can emerge as a viable solution to society's energy demand. Particularly in artificial photosynthesis, the catalytic chemistry that converts energy in the form of electricity into carbon‐based fuels and chemicals has yet to be developed. Here, we describe the foundational work and future prospects of an emerging and promising class of materials: metal‐ and covalent‐organic frameworks (MOFs and COFs). Within this context, these porous and tuneable framework materials have achieved initial success in converting abundant feedstocks (H2O and CO2) into chemicals and fuels. In this review, we first highlight key achievements in this direction. We then follow with a perspective on precisely how MOFs and COFs can perform in ways not possible with conventional molecular or heterogeneous catalysts. We conclude with a view on how spectroscopically probing MOF and COF catalysis can be used to elucidate reaction mechanisms and material dynamics throughout the course of reaction.

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“…They also confirm that the diazoniumelectrografting strategy is a viable approach to functionalizing ITO surfaces with stable and highly robust molecular layers. [11][12][13] It should be noted, however, that the   value is strongly dependent on the nature of the immobilized molecule. In the case of Fc-NHCO,   is equivalent to ~13 saturated monolayers of Fc-NH 2 on a planar electrode, which, once compared to the ~65 surface enhancement of the 1 m-thick nanostructured GLAD-ITO film, leads to the conclusion that only 20% of a saturated monolayer is covering the three-dimensional surface.…”

Section: Electrochemical Characterization Of Amidoferrocenementioning

confidence: 99%

“…A better alternative, which has recently emerged in the literature for the surface-functionalization of meso-TCEs, is to take advantage of the covalent electrochemical grafting of aryl-diazonium salts. [11][12][13] This method is highly versatile, simple, efficient and able to operate with a wide range of metal oxide surfaces. Also, because this is an electrodeposition approach, it offers the additional advantage of reliably grafting molecules on conductive surfaces, regardless of their shapes and porosities.…”

Section: Introductionmentioning

confidence: 99%

“…The method was successfully applied to the robust surface modification of meso-TCE electrodes with redox active dyes, leading to improved stability under hydrolytic aqueous conditions as compared to other surface functionalization chemistries. [11][12][13] Herein, we prepare robust GLAD-ITO electrodes pre-functionalized with carboxylate moieties through the electrochemical reduction of aryl diazonium salts. The resulting pre-functionalized electrodes are then used as a versatile platform for further covalent immobilization of the bioreceptor hemoglobin I from Lucina pectinata.…”

Section: Introductionmentioning

confidence: 99%

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An optical H2S biosensor based on the chemoselective Hb-I protein tethered to a transparent, high surface area nanocolumnar electrode

Dulac

Melet

Harris

et al. 2019

Sensors and Actuators B: Chemical

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Sensitive and selective detection of analytes in complex biological fluids can be an extremely challenging issue. The constructive association of biomolecules and transparent mesoporous electrodes is of interest in this area, as it can lead to innovative biosensors combining optical and electrochemical detection modes. This concept, however, requires the development of appropriate surface functionalization methodologies that are robust enough for long-term operation in physiological environments. In the present work, the high-surface area of 3D transparent mesoporous indium-tin oxide (ITO) electrodes (prepared by glancing angle deposition or GLAD) has been chemically functionalized with recombinant hemoglobin I from Lucina pectinata according to a versatile 2-step process. First, 4-diazoniumbenzoic acid salt is covalently electrografted onto the ITO surface, followed by amide coupling of the protein. The resulting electrodes were quantitatively characterized by cyclic voltammetry and UV-visible absorption spectroscopy, demonstrating high surface coverages (up to 45% of a closed-packed monolayer for Hemoglobin-I) and homogeneous distribution across the entire thickness of the GLAD mesoporous structure. Good stability is also observed when the modified electrodes are immersed for prolonged times in a high ionic strength saline buffer. We also show that the hemoglobin I-modified electrode can be used as an optical biosensor for the selective, reversible, and fast detection of H 2 S in aqueous solutions over a two-decade concentration range and with a limit of detection of 0.35 M. Good analytical performance was also achieved in human plasma without significant interference from the biological matrix.

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Robust electrografted interfaces on metal oxides for electrocatalysis – an in situ spectroelectrochemical study

Abstract: In situ spectroelectrochemistry demonstrates stability of electrografted diazonium interfaces on conductive oxides & their suitability as anchoring groups for molecular species.

Cited by 37 publications

References 82 publications

Surface Chemistry Modulates CO2 Reduction Reaction Intermediates on Silver Nanoparticle Electrocatalysts

Surface Chemistry Modulates CO2 Reduction Reaction Intermediates on Silver Nanoparticle Electrocatalysts

Artificial photosynthesis with metal and covalent organic frameworks (MOFs and COFs): challenges and prospects in fuel‐forming electrocatalysis

An optical H2S biosensor based on the chemoselective Hb-I protein tethered to a transparent, high surface area nanocolumnar electrode

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