Photoelectrochemical Methods for the Determination of the Flat-Band Potential in Semiconducting Photocatalysts: A Comparison Study

Koshevoy, Evgeny; Gribov, Evgeny; Polskikh, Danil; Lyulyukin, Mikhail; Solovyeva, Maria; Cherepanova, Svetlana; Kozlov, Denis; Selishchev, Dmitry

doi:10.1021/acs.langmuir.3c01158

Cited by 15 publications

(9 citation statements)

References 96 publications

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“…E MS values were found to differ significantly from those of other methods. Apparently, the MS method is not applicable in our case for various reasons, which may include the influence of particle size, the influence of the FTO substrate, the presence of two phases with different characteristics and morphology and others [59][60][61]. In the OCP method, as was shown earlier [60], the determined potential can be limited by defect levels below the conduction band, at which rapid recombination occurs.…”

Section: Flat-band Potential Determinationmentioning

confidence: 90%

“…Apparently, the MS method is not applicable in our case for various reasons, which may include the influence of particle size, the influence of the FTO substrate, the presence of two phases with different characteristics and morphology and others [59][60][61]. In the OCP method, as was shown earlier [60], the determined potential can be limited by defect levels below the conduction band, at which rapid recombination occurs. We previously suggested that, for TiO 2 -N samples, methanol additions reduce the degree of recombination due to an interaction with holes, and the detected E OCP becomes close to the E POP corresponding to E FB [60].…”

Section: Flat-band Potential Determinationmentioning

confidence: 90%

“…In the OCP method, as was shown earlier [60], the determined potential can be limited by defect levels below the conduction band, at which rapid recombination occurs. We previously suggested that, for TiO 2 -N samples, methanol additions reduce the degree of recombination due to an interaction with holes, and the detected E OCP becomes close to the E POP corresponding to E FB [60]. Previously, we also showed that the POP method for monophase samples can be recommended as the principal one for measuring E FB [60].…”

Section: Flat-band Potential Determinationmentioning

confidence: 97%

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Flat-Band Potential Determination and Catalytical Properties of Sn3O4/SnO2 Heterostructures in the Photo-Electrooxidation of Small Organic Molecules under Ultraviolet (370 nm) and Blue (450 nm) Light

Gribov,

Koshevoy,

Kuznetsov

et al. 2023

Materials

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Sn3O4 are promising semiconductor materials due to their visible light absorption ability. In this work, a series of materials, such as SnO2, Sn3O4 and Sn3O4/SnO2 heterostructures, with different phase ratios were prepared using hydrothermal synthesis. The materials were characterized using X-ray diffraction (XRD), Raman and diffuse reflectance spectroscopy (DRS), high resolution transmission electron microscopy (HRTEM), nitrogen adsorption (BET). Flat-band potentials (EFB) of the samples were determined using the photocurrent onset potential (POP) method. It was shown that the potentials obtained with open circuit potential measurements versus illumination intensity (OCP) likely corresponded to the EFB of SnO2 nanoparticles in heterostructures due to interfacial electron transfer from the conducting band of Sn3O4 to that of SnO2. The photo-electrooxidation processes of a series of organic substrates were studied in the potential range of 0.6–1.4 V vs. RHE under irradiation with ultraviolet (λ = 370 nm) and visible (λ = 450 nm) light. The Sn3O4 sample showed high activity in the photo-electrooxidation of acetone and formic acid in visible light. The Sn3O4/SnO2 samples exhibited noticeable activity only in the oxidation of formic acid. The presence of the SnO2 phase in the Sn3O4/SnO2 samples increased the photocurrent values under ultraviolet illumination, but significantly reduced the oxidation efficiency in visible light.

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Section: Flat-band Potential Determinationmentioning

confidence: 90%

Section: Flat-band Potential Determinationmentioning

confidence: 90%

Section: Flat-band Potential Determinationmentioning

confidence: 97%

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Flat-Band Potential Determination and Catalytical Properties of Sn3O4/SnO2 Heterostructures in the Photo-Electrooxidation of Small Organic Molecules under Ultraviolet (370 nm) and Blue (450 nm) Light

Gribov,

Koshevoy,

Kuznetsov

et al. 2023

Materials

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“…In other words, the positions of the CB and VB determine how feasible a given photocatalytic reaction can be. For the determination of flat-band ( E FB ) potential, and consequently CB and VB values, various approaches are found in the literature, , such as Mott–Schottky, , illuminated chronopotentiometry, the Butler and Ginley relationship, among others. Each of these methods has its limitations and pitfalls, with the values obtained capable of exhibiting significant variation within the same sample depending on the technique used.…”

Section: Strategies To Enhance Carbon Nitride Photoelectrochemical Pe...mentioning

confidence: 99%

“…Each of these methods has its limitations and pitfalls, with the values obtained capable of exhibiting significant variation within the same sample depending on the technique used. Selishchev and co-workers reported four different methods to determine the E FB of the same sample of PCN synthesized from the pyrolysis of urea . The techniques included Mott–Schottky, illuminated chronopotentiometry, photocurrent onset, and Gartner–Butler.…”

Section: Strategies To Enhance Carbon Nitride Photoelectrochemical Pe...mentioning

confidence: 99%

Carbon Nitrides in Photoelectrochemistry: State of the Art and Perspectives Beyond Water Splitting

Blaskievicz,

Francisco,

Marken

et al. 2024

ACS Appl. Energy Mater.

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Photoelectrodes made from cost-effective materials are the most desired for practical photoelectrochemical (PEC) applications, aiming to help in the imminent environmental crisis that urges an energetic transition. A prominent class of semiconductors are the polymeric carbon nitrides (PCN), which appear to be an eco-friendly solution particularly for green hydrogen production through water splitting, value-added organic compounds obtention from biomass upgrading, or CO 2 reduction; even green ammonia can be obtained by PEC reduction of N 2 . In this sense, monitoring dangerous environmental species or converting them into less toxic ones can also be performed through PEC using carbon nitridebased electrodes. In this review, we provide an overview of the basics of PCN applications in PEC, including commonly employed strategies to enhance their performance. Additionally, we discuss the current state-of-the-art for PCN in PEC water splitting as well as lesser-explored areas such as biomass upgrading, environmental remediation, photoelectroanalytical sensing, and light-driven CO 2 and N 2 reduction reactions. Finally, we present an overview of prospects for PCN material in PEC.

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Polymerization Improvement of Graphitic Carbon Nitride Films Derived from Melamine and Thiourea

Oo,

Zhao,

Baqi

et al. 2024

Small

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Deposition of low‐cost, efficient, and environmentally friendly graphitic carbon nitride (g‐CN) films as photoanodes is a crucial step for constructing photoelectrochemical (PEC) cells and exploring their PEC performance. Currently, the improvement of the photocurrent density of g‐CN films is badly needed for their practical applications in PEC water splitting. Enhancing the g‐CN crystallinity by optimizing their synthesis conditions only through screening appropriate reactant precursors is insufficient for this purpose. Herein, using melamine and thiourea precursors with mass ratio 5:1, the degree of polymerization of g‐CN thin films is successfully improved by a thermal vapor condensation method. The obtained pure g‐CN exhibits a remarkably enhanced photocurrent density of 404.4 µA cm−2 at 1.23 V versus reversible hydrogen electrodes. Theoretical calculations reveal that the continuous attachment of small carbodiimide (HN═C═NH) mainly generated by thiourea to the melamine matrix facilitates the formation of large‐area conjugated structure, which fundamentally determines better charge carrier separation and transfer thereby enhancing the PEC performance. This work realizes the synthesis of well‐polymerized g‐CN films with improved PEC activity and offers a computational understanding for the nucleation and growth mechanism of the polycrystalline g‐CN.

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Photoelectrochemical Methods for the Determination of the Flat-Band Potential in Semiconducting Photocatalysts: A Comparison Study

Cited by 15 publications

References 96 publications

Flat-Band Potential Determination and Catalytical Properties of Sn3O4/SnO2 Heterostructures in the Photo-Electrooxidation of Small Organic Molecules under Ultraviolet (370 nm) and Blue (450 nm) Light

Flat-Band Potential Determination and Catalytical Properties of Sn3O4/SnO2 Heterostructures in the Photo-Electrooxidation of Small Organic Molecules under Ultraviolet (370 nm) and Blue (450 nm) Light

Carbon Nitrides in Photoelectrochemistry: State of the Art and Perspectives Beyond Water Splitting

Polymerization Improvement of Graphitic Carbon Nitride Films Derived from Melamine and Thiourea

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