Molecular level insight on the adsorption of carboxylic acids to oxide nanoparticles in aqueous solution by X-ray photoelectron spectroscopy

Olivieri, Giorgia; Goel, Alok; Brown, Matthew A.

doi:10.1039/c5cc10582j

Cited by 10 publications

(5 citation statements)

References 29 publications

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“…We rationalize the above trend through recognition of the dominant surface interaction mechanism between (hydroxylated) silica surfaces and polar-protic molecules. Such interactions are governed by surface–adsorbate hydrogen-bonding interactions, which provide not only a favorable bonding mode between protic adsorbates and surface-bound hydroxyl groups , but also a well-established means for proton exchange. − Exchange interactions during the encoding periods of T 1 – T 2 correlation measurements have significant potential to bias the resulting relaxation characteristics. This concept is elucidated by considering two coupled magnetization reservoirs, M sol and M ads , which we associate with solid-bound and adsorbate-bound hydroxyl protons, respectively.…”

Section: Resultsmentioning

confidence: 99%

Low-Field Functional Group Resolved Nuclear Spin Relaxation in Mesoporous Silica

Robinson

May

Johns

2021

ACS Appl. Mater. Interfaces

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Solid-fluid interactions underpin the efficacy of functional porous materials across a diverse array of chemical reaction and separation processes. Here we report low magnetic field 2D 1 H nuclear spin relaxation measurements as a non-invasive probe of adsorbate identity and interfacial dynamics within such systems.For the first time, we demonstrate the capacity of this approach in distinguishing functional group-specific relaxation phenomena across a diverse range of alcohols and carboxylic acids employed as solvents, reagents and liquid hydrogen carriers, with distinct relaxation responses assigned to the alkyl and hydroxyl moieties of each confined liquids. Uniquely, this relaxation behaviour is shown to correlate with adsorbate acidity, with the observed relationship rationalised on the basis of surface-adsorbate proton exchange dynamics. Our results demonstrate that nuclear spin relaxation provides a molecular-level perspective on sorbent/sorbate interactions, motivating the exploration of such measurements as a unique probe of adsorbate identity within optically opaque porous media.

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Section: Resultsmentioning

confidence: 99%

Low-Field Functional Group Resolved Nuclear Spin Relaxation in Mesoporous Silica

Robinson

May

Johns

2021

ACS Appl. Mater. Interfaces

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“…[68][69][70][71] In addition, the results of liquid-phase X-ray photoelectron spectroscopy (XPS) and AFM analysis were reported to analyze the protonation phenomenon and complex structure of carboxyl groups on the surface of nanoparticles, and also to analyze the adsorption of protein and its isoelectric point on solid surfaces. [72][73][74] However, the analysis of the interfacial specificity of ions and molecules at solid-liquid interfaces suffers from the limitation that measurements are very challenging due to the random motility and noise effects of molecules and ions in liquids, which is why only a few techniques such as sum frequency spectroscopy and XPS have been proposed in the last decades. 75,76 Furthermore, various studies have reported the analysis of ionic behavior at interfaces in diverse fields such as chemical/biological sensors, energy harvesting, and batteries.…”

Section: Experimental Aspectsmentioning

confidence: 99%

“…The results of interfacial characterization using traditional atomic force microscope (AFM)‐based analytical techniques such as liquid AFM and Kelvin probe force microscopy (KPFM) are continuously being reported in related fields 68–71 . In addition, the results of liquid‐phase X‐ray photoelectron spectroscopy (XPS) and AFM analysis were reported to analyze the protonation phenomenon and complex structure of carboxyl groups on the surface of nanoparticles, and also to analyze the adsorption of protein and its isoelectric point on solid surfaces 72–74 …”

Section: Scalability Of Ionovoltaic Researchmentioning

confidence: 99%

Ionovoltaics in energy harvesting and applications: A journey from early development to current state‐of‐the‐art

Lee,

Park,

Yoon

et al. 2023

EcoMat

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Ionovoltaics is a breakthrough concept in energy conversion that harnesses water motion with ion dynamics to generate electrical energy. This phenomenon is based on the interaction between the nanoscopic ionic behavior at the solid–liquid interface and the flow of electrons in a semiconductor electrode. Ionovoltaic research aims to present the most rational and convincing mechanism for the much‐debated principle of energy conversion by water motion through a deeper understanding of solid–liquid interfacial phenomena and to discuss the potential to transform related fields through the development of enabling technologies such as novel energy harvesters, interfacial analysis tools, and bio/chemical sensors. Furthermore, efforts to develop high‐efficiency ionovoltaic device powered by small water droplets indicate a potential contribution to the advancement of green energy systems that complement solar and wind power generation and address environmental pollution and energy shortages. This review paper explores the evolution of energy harvesting technologies using water motion, with a particular focus on ionovoltaics as an emerging field. By establishing the fundamentals, this study investigates solid–liquid interfaces, semiconductor properties, and natural water motion‐driven ionovoltaic phenomena and also highlights that extensive research on complex ion/interface phenomena can have practical applications in diverse industrial fields.image

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“…Such interactions are governed by surface-adsorbate hydrogen bonding interactions, which provide not only a favourable bonding mode between protic adsorbates and surface-bound hydroxyl groups, 57,58 but also a well-established means for proton exchange. [59][60][61] Exchange interactions during the encoding periods of 1 − 2 correlation measurements have significant potential to bias the resulting relaxation characteristics. This concept is elucidated by considering two coupled magnetisation reservoirs, and , which we associate with solid-bound and adsorbate-bound hydroxyl protons, respectively.…”

Section: Relaxation Acidity and Surface-adsorbate Proton Exchangementioning

confidence: 99%

Functional Group Resolved Nuclear Spin Relaxation in Porous Media

Robinson

May²,

Johns³

2021

Preprint

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Understanding solid-fluid interactions within porous materials is critical for their efficient utilisation across chemical reaction and separation processes. However, detailed characterisation of interfacial phenomena within such systems is hampered by their optically opaque nature. Motivated by the need to bridge this capability gap, we detail here the application of low magnetic field 2D <sup>1</sup>H nuclear spin relaxation measurements as a non-invasive probe of sorbate/sorbent interactions, exploring the relaxation characteristics exhibited by liquid adsorbates confined to a model mesoporous silica. For the first time, we demonstrate the capacity of such measurements to distinguish functional group-specific relaxation phenomena across a diverse range of protic adsorbates of wide importance as solvents, reagents, and hydrogen carriers, with distinct relaxation environments assigned to the alkyl and hydroxyl moieties of the confined liquids. Uniquely, this relaxation behaviour is shown to correlate with adsorbate acidity, with the observed relationship rationalised on the basis of surface-adsorbate proton exchange dynamics.

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Molecular level insight on the adsorption of carboxylic acids to oxide nanoparticles in aqueous solution by X-ray photoelectron spectroscopy

Cited by 10 publications

References 29 publications

Low-Field Functional Group Resolved Nuclear Spin Relaxation in Mesoporous Silica

Low-Field Functional Group Resolved Nuclear Spin Relaxation in Mesoporous Silica

Ionovoltaics in energy harvesting and applications: A journey from early development to current state‐of‐the‐art

Functional Group Resolved Nuclear Spin Relaxation in Porous Media

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