Quantifying Losses and Assessing the Photovoltage Limits in Metal–Insulator–Semiconductor Water Splitting Systems

Hemmerling, John; Quinn, Joseph P.; Linic, Suljo

doi:10.1002/aenm.201903354

Cited by 36 publications

(83 citation statements)

References 64 publications

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“…This also can affect the recombination rates and impact the photovoltage. [4,[31][32][33][34] iv) The geometry of the interfacial contact area will also modulate the transfer of charge carriers across the interface, i.e., the rate of the collection of charge carriers by the EC is affected by the interfacial contact EC/SC area. [35] To test whether the barrier height is different for the oxidized Si interface in contact with Ni compared to the non-oxidized Si/Ni interface (mechanisms i and ii above), we performed the Mott-Schottky analysis (see Supporting Information for details).…”

Section: Physical Electrochemical and Atomistic Characterization Of P...mentioning

confidence: 99%

“…To describe and quantify how these atomistic changes to the EC/SC interface impact the system performance, we developed an analytical model that can capture the behavior of the systems. The model is based on the illuminated diode equation, in which the relationship between the photovoltage (V ph ) and the net current (J net ) through an EC/SC interface is given by the following expression: [31] ln…”

Section: Modeling Of the Photoelectrocatalysts Behaviormentioning

confidence: 99%

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Characterizing the Geometry and Quantifying the Impact of Nanoscopic Electrocatalyst/Semiconductor Interfaces under Solar Water Splitting Conditions

Hemmerling

Mathur

Linic

2022

Advanced Energy Materials

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The materials that are receiving the most attention in photoelectrochemical water splitting are metallic nanoparticle electrocatalysts (np‐EC) attached to the surface of a semiconductor (SC) light absorber. In these multicomponent systems, the interface between the semiconductor and electrocatalysts critically affects performance. However, the np‐EC/SC interface remains poorly understood as it is complex on atomic scales, dynamic under reaction conditions, and inaccessible to direct experimental probes. This contribution sheds light on how the electrocatalyst/semiconductor interface evolves under reaction conditions by investigating the behavior of nickel electrocatalysts (as nanoparticles and films) deposited on silicon semiconductors. Rigorous electrochemical experiments, interfacial atomistic characterization, and computational modeling are combined to demonstrate critical links between the atomistic features of the interface and the overall performance. It is shown that electrolyte‐induced atomistic changes to the interface lead to (1) modulation of the charge carrier fluxes and a dramatic decrease in the electron/hole recombination rates and (2) a change in the barrier height of the interface. Furthermore, the critical roles of nonidealities and electrocatalyst coverage due to interfacial geometry are explored. Each of these factors must be considered to optimize the design of metal/semiconductor interfaces which are broadly applicable to photoelectrocatalysis and photovoltaic research.

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Section: Physical Electrochemical and Atomistic Characterization Of P...mentioning

confidence: 99%

Section: Modeling Of the Photoelectrocatalysts Behaviormentioning

confidence: 99%

Characterizing the Geometry and Quantifying the Impact of Nanoscopic Electrocatalyst/Semiconductor Interfaces under Solar Water Splitting Conditions

Hemmerling

Mathur

Linic

2022

Advanced Energy Materials

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“…Interestingly, the surface dipole induced by the chemical interaction; in other words, the replacement of hydroxyl groups with electron-withdrawing phosphonate groups strongly affects the surface [95][96][97]. And the phenyl moieties with various substituents change the higher electron-withdrawing abilities also increase the surface generated dipole [98,99] to change the barrier height at the interface (Figure 4b).…”

Section: Modulation Of Solid-solid Interface For Charge Transfer and mentioning

confidence: 99%

“…When the barrier height is small, thermionic emission charge transfer is dominant, while intraband tunneling occurs when the barrier height is large. Therefore, the characteristic charge transfer distance has a reverse-volcano relationship with the surface dipole and the barrier height [99]. Insertion of organic molecules at the solid-solid interface changes the charge transfer mechanism to Z-scheme charge transfer by band bending modulation at the interface.…”

Section: Modulation Of Solid-solid Interface For Charge Transfer and mentioning

confidence: 99%

Understanding Surface Modulation to Improve the Photo/Electrocatalysts for Water Oxidation/Reduction

Cho

Lee

2020

Molecules

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Water oxidation and reduction reactions play vital roles in highly efficient hydrogen production conducted by an electrolyzer, in which the enhanced efficiency of the system is apparently accompanied by the development of active electrocatalysts. Solar energy, a sustainable and clean energy source, can supply the kinetic energy to increase the rates of catalytic reactions. In this regard, understanding of the underlying fundamental mechanisms of the photo/electrochemical process is critical for future development. Combining light-absorbing materials with catalysts has become essential to maximizing the efficiency of hydrogen production. To fabricate an efficient absorber-catalysts system, it is imperative to fully understand the vital role of surface/interface modulation for enhanced charge transfer/separation and catalytic activity for a specific reaction. The electronic and chemical structures at the interface are directly correlated to charge carrier movements and subsequent chemical adsorption and reaction of the reactants. Therefore, rational surface modulation can indeed enhance the catalytic efficiency by preventing charge recombination and prompting transfer, increasing the reactant concentration, and ultimately boosting the catalytic reaction. Herein, the authors review recent progress on the surface modification of nanomaterials as photo/electrochemical catalysts for water reduction and oxidation, considering two successive photogenerated charge transfer/separation and catalytic chemical reactions. It is expected that this review paper will be helpful for the future development of photo/electrocatalysts.

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“…Studies in the last decade have shown that chemical dynamics along the excited‐state PESs are accessible in plasmonic and hybrid plasmonic catalytic systems through localized surface plasmon resonance (LSPR)‐mediated electronic excitations. [ 2–20,22–34 ] The hybrid plasmonic photocatalytic approach is attractive for the conversion of solar energy into chemical energy, the development of coke‐resistant and selective catalytic processes, and the distributed synthesis of valuable chemicals with little to no requirement of external heating. [ 2–20,35,36 ] For example, Cu–Fe hybrid plasmonic nanocatalysts under visible‐light excitation exhibit high activity for ammonia (NH 3 ) synthesis at lower temperatures (30–42 °C) and atmospheric pressure, as compared to the Haber–Bosch process.…”

Section: Introductionmentioning

confidence: 99%

Photoinduced Electron and Energy Transfer Pathways and Photocatalytic Mechanisms in Hybrid Plasmonic Photocatalysis

Ramakrishnan

Mohammadparast

Dadgar

et al. 2021

Advanced Optical Materials

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Hybrid plasmonic nanostructures are built on plasmonic metalnanostructures surrounded by catalytic metals or metal oxides. Recent studies have shown that hybrid plasmonic nanocatalysts can concurrently utilize thermal energy and photon stimuli and exhibit high catalytic activity, selectivity, and stability that are not attainable in conventional purely thermally activated catalytic processes. The hybrid plasmonic photocatalytic approach has recently emerged as an attractive concept for the conversion of solar energy into chemical energy, the distributed synthesis of valuable chemicals such as ammonia with little to no requirement of external heating, and the development of coke‐resistant and selective catalytic processes. The field of hybrid plasmonic photocatalysis has grown tremendously in the last decade. In this review article, the advantages of visible‐light‐augmented hybrid plasmonic photocatalysis over conventional pure thermally activated heterogeneous catalysis are discussed. Fundamental insights are provided into photocatalytic mechanisms by which the photoexcited charge carriers (electrons and holes) are formed and transferred to adsorbates triggering chemical transformations on the surface of hybrid plasmonic nanocatalysts. Computational modeling used for predicting and understanding the photocatalytic activity and selectivity on hybrid plasmonic nanostructures is also reviewed. The review closes with a discussion of the current challenges, new opportunities, and future outlook for hybrid plasmonic photocatalysis.

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Quantifying Losses and Assessing the Photovoltage Limits in Metal–Insulator–Semiconductor Water Splitting Systems

Cited by 36 publications

References 64 publications

Characterizing the Geometry and Quantifying the Impact of Nanoscopic Electrocatalyst/Semiconductor Interfaces under Solar Water Splitting Conditions

Characterizing the Geometry and Quantifying the Impact of Nanoscopic Electrocatalyst/Semiconductor Interfaces under Solar Water Splitting Conditions

Understanding Surface Modulation to Improve the Photo/Electrocatalysts for Water Oxidation/Reduction

Photoinduced Electron and Energy Transfer Pathways and Photocatalytic Mechanisms in Hybrid Plasmonic Photocatalysis

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