A Combination of EPR, Microscopy, Electrophoresis and Theory to Elucidate the Chemistry of W- and N-Doped TiO<sub>2</sub> Nanoparticle/Water Interfaces

The doping of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">i</mi><msub><mi mathvariant="...

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Autores principales:	Sam Gorman, Kirstie Rickaby, Li Lu, Christopher J. Kiely, Donald E. Macphee, Andrea Folli
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	electron paramagnetic resonance semiconductor photocatalysis TiO<sub>2</sub> colloidal chemistry solid-liquid interface metal oxides Chemical technology TP1-1185 Chemistry QD1-999
Acceso en línea:	https://doaj.org/article/397a291b398a4e68b4e1f8089cbdad2a
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spelling	oai:doaj.org-article:397a291b398a4e68b4e1f8089cbdad2a2021-11-25T17:05:39ZA Combination of EPR, Microscopy, Electrophoresis and Theory to Elucidate the Chemistry of W- and N-Doped TiO<sub>2</sub> Nanoparticle/Water Interfaces10.3390/catal111113052073-4344https://doaj.org/article/397a291b398a4e68b4e1f8089cbdad2a2021-10-01T00:00:00Zhttps://www.mdpi.com/2073-4344/11/11/1305https://doaj.org/toc/2073-4344The doping of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">i</mi><msub><mi mathvariant="normal">O</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula>-based nanomaterials for semiconductor-sensitised photoreactions has been a practice extensively studied and applied for many years. The main goal remains the improvement of light harvesting capabilities under passive solar irradiation, that in the case of undoped <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">i</mi><msub><mi mathvariant="normal">O</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula> is limited and restricted to relatively low latitudes. The activity and selectivity of doped <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">i</mi><msub><mi mathvariant="normal">O</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula> photocatalysts are generally discussed on the basis of the modified band structure; energetics of intrinsic or extrinsic band gaps including trapping states; redox potentials of band edges, including band bending at solid/fluid interfaces; and charge carriers scavenging/transfer by/to adsorbed species. Electron (and hole) transfer to adsorbates is often invoked to justify the formation of highly reactive species (e.g., <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">H</mi><msup><mi mathvariant="normal">O</mi><mo>.</mo></msup></mrow></semantics></math></inline-formula> from water); however, a complete description of the nanoparticle surface chemistry dictating adsorption/desorption events is often missing or overlooked. Here, we show that by employing a surface electrochemical triple-layer (TLM) approach for the nanoparticles/water interface, in combination with electron paramagnetic resonance spectroscopy (EPR), transmission electron microscopy and electrophoretic measurements, we can elucidate the surface chemistry of doped <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">i</mi><msub><mi mathvariant="normal">O</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula> nanoparticles and link it to the nature of the dopants. Exemplifying it for the cases of undoped, as well as W- and N-doped and codoped <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">i</mi><msub><mi mathvariant="normal">O</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula> nanoparticles, we show how surface charge density; surface, Stern and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mi>ζ</mi></semantics></math></inline-formula> potentials; surface acidity constants; and speciation of surface sites are influenced by the nature of the dopants and their loading.Sam GormanKirstie RickabyLi LuChristopher J. KielyDonald E. MacpheeAndrea FolliMDPI AGarticleelectron paramagnetic resonancesemiconductor photocatalysisTiO<sub>2</sub>colloidal chemistrysolid-liquid interfacemetal oxidesChemical technologyTP1-1185ChemistryQD1-999ENCatalysts, Vol 11, Iss 1305, p 1305 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	electron paramagnetic resonance semiconductor photocatalysis TiO<sub>2</sub> colloidal chemistry solid-liquid interface metal oxides Chemical technology TP1-1185 Chemistry QD1-999
spellingShingle	electron paramagnetic resonance semiconductor photocatalysis TiO<sub>2</sub> colloidal chemistry solid-liquid interface metal oxides Chemical technology TP1-1185 Chemistry QD1-999 Sam Gorman Kirstie Rickaby Li Lu Christopher J. Kiely Donald E. Macphee Andrea Folli A Combination of EPR, Microscopy, Electrophoresis and Theory to Elucidate the Chemistry of W- and N-Doped TiO<sub>2</sub> Nanoparticle/Water Interfaces
description	The doping of <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">i</mi><msub><mi mathvariant="normal">O</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula>-based nanomaterials for semiconductor-sensitised photoreactions has been a practice extensively studied and applied for many years. The main goal remains the improvement of light harvesting capabilities under passive solar irradiation, that in the case of undoped <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">i</mi><msub><mi mathvariant="normal">O</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula> is limited and restricted to relatively low latitudes. The activity and selectivity of doped <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">i</mi><msub><mi mathvariant="normal">O</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula> photocatalysts are generally discussed on the basis of the modified band structure; energetics of intrinsic or extrinsic band gaps including trapping states; redox potentials of band edges, including band bending at solid/fluid interfaces; and charge carriers scavenging/transfer by/to adsorbed species. Electron (and hole) transfer to adsorbates is often invoked to justify the formation of highly reactive species (e.g., <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">H</mi><msup><mi mathvariant="normal">O</mi><mo>.</mo></msup></mrow></semantics></math></inline-formula> from water); however, a complete description of the nanoparticle surface chemistry dictating adsorption/desorption events is often missing or overlooked. Here, we show that by employing a surface electrochemical triple-layer (TLM) approach for the nanoparticles/water interface, in combination with electron paramagnetic resonance spectroscopy (EPR), transmission electron microscopy and electrophoretic measurements, we can elucidate the surface chemistry of doped <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">i</mi><msub><mi mathvariant="normal">O</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula> nanoparticles and link it to the nature of the dopants. Exemplifying it for the cases of undoped, as well as W- and N-doped and codoped <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">i</mi><msub><mi mathvariant="normal">O</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula> nanoparticles, we show how surface charge density; surface, Stern and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mi>ζ</mi></semantics></math></inline-formula> potentials; surface acidity constants; and speciation of surface sites are influenced by the nature of the dopants and their loading.
format	article
author	Sam Gorman Kirstie Rickaby Li Lu Christopher J. Kiely Donald E. Macphee Andrea Folli
author_facet	Sam Gorman Kirstie Rickaby Li Lu Christopher J. Kiely Donald E. Macphee Andrea Folli
author_sort	Sam Gorman
title	A Combination of EPR, Microscopy, Electrophoresis and Theory to Elucidate the Chemistry of W- and N-Doped TiO<sub>2</sub> Nanoparticle/Water Interfaces
title_short	A Combination of EPR, Microscopy, Electrophoresis and Theory to Elucidate the Chemistry of W- and N-Doped TiO<sub>2</sub> Nanoparticle/Water Interfaces
title_full	A Combination of EPR, Microscopy, Electrophoresis and Theory to Elucidate the Chemistry of W- and N-Doped TiO<sub>2</sub> Nanoparticle/Water Interfaces
title_fullStr	A Combination of EPR, Microscopy, Electrophoresis and Theory to Elucidate the Chemistry of W- and N-Doped TiO<sub>2</sub> Nanoparticle/Water Interfaces
title_full_unstemmed	A Combination of EPR, Microscopy, Electrophoresis and Theory to Elucidate the Chemistry of W- and N-Doped TiO<sub>2</sub> Nanoparticle/Water Interfaces
title_sort	combination of epr, microscopy, electrophoresis and theory to elucidate the chemistry of w- and n-doped tio<sub>2</sub> nanoparticle/water interfaces
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/397a291b398a4e68b4e1f8089cbdad2a
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A Combination of EPR, Microscopy, Electrophoresis and Theory to Elucidate the Chemistry of W- and N-Doped TiO<sub>2</sub> Nanoparticle/Water Interfaces

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