Photoelectrochemical Behavior of n-type Si(100) Electrodes Coated with Thin Films of Manganese Oxide Grown by Atomic Layer Deposition

Strandwitz, Nicholas C.; Comstock, David J.; Grimm, Ronald L.; Nielander, Adam C.; Elam, Jeffrey W.; Lewis, Nathan S.

doi:10.1021/jp311207x

Cited by 136 publications

(141 citation statements)

References 51 publications

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“…[ 65,66 ] Moreover, several laboratories, including our own, have recently demonstrated that layers of TiO 2 can stabilize photoelectrodes against corrosion. [67][68][69][70][71][72] To summarize our theoretical fi ndings: There is a thermodynamic driving force for TiO 2 to selectively segregate to the undercoordinated sites, which are most prone to dissolution, due to its favorable surface formation energy. This should lead to an overall stabilization of the surface, since TiO 2 is stable in acid up to more than 2.1 V RHE .…”

Section: Theoretical Calculationsmentioning

confidence: 94%

Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti‐Stabilized MnO₂

Frydendal

Paoli

Chorkendorff

et al. 2015

Advanced Energy Materials

197

180

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Catalysts are required for the oxygen evolution reaction, which are abundant, active, and stable in acid. MnO2 is a promising candidate material for this purpose. However, it dissolves at high overpotentials. Using first‐principles calculations, a strategy to mitigate this problem by decorating undercoordinated surface sites of MnO2 with a stable oxide is developed here. TiO2 stands out as the most promising of the different oxides in the simulations. This prediction is experimentally verified by testing sputter‐deposited thin films of MnO2 and Ti–MnO2. A combination of electrochemical measurements, quartz crystal microbalance, inductively coupled plasma mass spectrometry measurements, and X‐ray photoelectron spectroscopy is performed. Small amounts of TiO2 incorporated into MnO2 lead to a moderate improvement in stability, with only a small decrease in activity. This study opens up the possibility of engineering surface properties of catalysts so that active and abundant nonprecious metal oxides can be used in acid electrolytes.

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Section: Theoretical Calculationsmentioning

confidence: 94%

Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti‐Stabilized MnO₂

Frydendal

Paoli

Chorkendorff

et al. 2015

Advanced Energy Materials

197

180

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“…Under water oxidation conditions,narrow-band-gap semiconductors are thermodynamically prone to self-oxidation, forming insulating oxides that block the transfer of photogenerated carriers.The photocurrent density of bare n-Si was essentially zero in strong alkaline solutions [22] or dropped to zero quickly during the second scan in neutral electrolytes. [23] Although transparent conductive oxides (TCOs) such as indium tin oxide (ITO) or fluorine-doped tin oxide (FTO) could protect the substrate against corrosion to some extent under neutral or mild pH conditions, [24] limited success with modified TCO has been reported for high pH solutions.…”

Section: Surface Protection For Photoanodesmentioning

confidence: 98%

“…Thus,t he Schottky junction at the semiconductor/solution interface is no longer required, which allowed the surface cocatalysts to be optimized independently.I na ddition, edge [24b] OER catalytic effect of b) NiO x , [32] c) CoO x , [33] and d) MnO [22] with . .…”

Section: Buried Junctions For Higher Photovoltage and Device Flexibilitymentioning

confidence: 99%

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Single‐Crystal Semiconductors with Narrow Band Gaps for Solar Water Splitting

2015

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Solar water splitting provides a clean and renewable approach to produce hydrogen energy. In recent years, single-crystal semiconductors such as Si and InP with narrow band gaps have demonstrated excellent performance to drive the half reactions of water splitting through visible light due to their suitable band gaps and low bulk recombination. This Minireview describes recent research advances that successfully overcome the primary obstacles in using these semiconductors as photoelectrodes, including photocorrosion, sluggish reaction kinetics, low photovoltage, and unfavorable planar substrate surface. Surface modification strategies, such as surface protection, cocatalyst loading, surface energetics tuning, and surface texturization are highlighted as the solutions.

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“…Mn [62], Fe [63], Ni [26,[64][65][66][67][68][69][70] and Ir [71], have been used to protect n-Si photoanodes for water oxidation in strongly alkaline or acidic electrolytes [72]. Protection of III-V and II-VI semiconductors in aqueous photoelectrochemical systems has also been studied.…”

Section: Introductionmentioning

confidence: 99%

Protection of inorganic semiconductors for sustained, efficient photoelectrochemical water oxidation

Lichterman

Sun

et al. 2016

Catalysis Today

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Small-band-gap (E g < 2 eV) semiconductors must be stabilized for use in integrated devices that convert solar energy into the bonding energy of a reduced fuel, specifically H 2 (g) or a reduced-carbon species such as CH 3 OH or CH 4 . To sustainably and scalably complete the fuel cycle, electrons must be liberated through the oxidation of water to O 2 (g). Strongly acidic or strongly alkaline electrolytes are needed to enable efficient and intrinsically safe operation of a full solar-driven water-splitting system. However, under water-oxidation conditions, the smallband-gap semiconductors required for efficient cell operation are unstable, either dissolving or forming insulating surface oxides. We describe herein recent progress in the protection of semiconductor photoanodes under such operational conditions. We specifically describe the properties of two protective overlayers, TiO 2 /Ni and NiO x , both of which have demonstrated the ability to protect otherwise unstable semiconductors for >100 h of continuous solar-driven water oxidation when in contact with a highly alkaline aqueous electrolyte (1.0 M KOH(aq)). The 2 stabilization of various semiconductor photoanodes is reviewed in the context of the electronic characteristics and a mechanistic analysis of the TiO 2 films, along with a discussion of the optical, catalytic, and electronic nature of NiO x films for stabilization of semiconductor photoanodes for water oxidation.

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Photoelectrochemical Behavior of n-type Si(100) Electrodes Coated with Thin Films of Manganese Oxide Grown by Atomic Layer Deposition

Abstract: Figure S1. XP spectra of the Si 2p region of MnO|Si photoelectrodes with 100 cycles (~10 nm) of MnO (filled circles and blue line) and 25 cycles (~2.5 nm) of MnO (open circles).

Cited by 136 publications

References 51 publications

Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti‐Stabilized MnO₂

Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti‐Stabilized MnO₂

Single‐Crystal Semiconductors with Narrow Band Gaps for Solar Water Splitting

Protection of inorganic semiconductors for sustained, efficient photoelectrochemical water oxidation

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Photoelectrochemical Behavior of n-type Si(100) Electrodes Coated with Thin Films of Manganese Oxide Grown by Atomic Layer Deposition

Abstract: Figure S1. XP spectra of the Si 2p region of MnO|Si photoelectrodes with 100 cycles (~10 nm) of MnO (filled circles and blue line) and 25 cycles (~2.5 nm) of MnO (open circles).

Cited by 136 publications

References 51 publications

Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti‐Stabilized MnO2

Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti‐Stabilized MnO2

Single‐Crystal Semiconductors with Narrow Band Gaps for Solar Water Splitting

Protection of inorganic semiconductors for sustained, efficient photoelectrochemical water oxidation

Contact Info

Product

Resources

About

Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti‐Stabilized MnO₂

Toward an Active and Stable Catalyst for Oxygen Evolution in Acidic Media: Ti‐Stabilized MnO₂