Photocatalytic water oxidation with iron oxide hydroxide (rust) nanoparticles

Shelton, Timothy L.; Bensema, Bronwyn L.; Brune, Nicholas K.; Wong, Christopher J.; Yeh, Max; Osterloh, Frank E.

doi:10.1117/1.jpe.7.012003

Cited by 8 publications

(4 citation statements)

References 36 publications

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“…Most of the iron-based electro-precatalysts evolve in situ to iron-oxy-hydroxides and behave as the reactive species for alkaline oxygen evolution reaction (OER). − Independently prepared polycrystalline FeO(OH) also can show superior OER activity under alkaline condition where the phase or crystallinity plays a crucial role. , Recent studies have also found that heteroatom doping in the FeO(OH) structure may lead to improve its OER activity. − Despite a controversy of the actual reactive metal, remarkable activity was seen with Fe x Ni 1– x O(OH). ,, Recent studies by Osterloh indicated that α- and γ-FeO(OH) materials can show photocatalytic water oxidation . Weinstock et al depicted further that POM-protected γ-FeO(OH) behaves as a soluble photocatalyst analogue of insoluble iron-oxy-hydroxide to show water oxidation .…”

Section: Resultsmentioning

confidence: 99%

“…23,27,28 Recent studies by Osterloh indicated that αand γ-FeO(OH) materials can show photocatalytic water oxidation. 47 Weinstock et al depicted further that POMprotected γ-FeO(OH) behaves as a soluble photocatalyst analogue of insoluble iron-oxy-hydroxide to show water oxidation. 31 In a similar line, Mallick and Chakraborty have recently shown that ca.…”

Section: Isolation Of Soluble Ni X Fe 1−x O(oh) Stabilized By [Mo 7 O...mentioning

confidence: 99%

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Stabilization of Nickel-Doped Iron-oxy-hydroxide Core in Water by Heptamolybdate Ions to Improve the Electrochemical Oxygen Evolution Reaction

Samanta,

Mallick,

Chakraborty

2023

ACS Appl. Energy Mater.

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Heterometal-doped nickel-oxy-hydroxides or high-entropy multimetallic oxides show notable electrocatalytic activity. Herein, a readily available Anderson-type polyoxometalate (POM) anion, heptamolybdate ([Mo 7 O 24 ] 6− ), is taken as an inorganic ligand to stabilize the nickel(II)-doped iron-oxy-hydroxide nanocore. [Mo 7 O 24 ] 6−ligated Ni x Fe 1−x O(OH) nanomaterials with different ratios of Ni(II) and Fe(III) in the core (1−3) are prepared via a hydrothermal route. ICP−MS and the subsequent PXRD study of the materials have found out that approximately 1.5−2% nickel is incorporated into the γ-FeO(OH) core without altering its two-dimensional-layered lattice structure. The presence of numerous POMs covalently linked on the surface of 4−5 nm highly crystalline Ni x Fe 1−x O(OH) core is proven by multiple spectroscopic and microscopic techniques. Negative zeta potential of 1−3 infers the ionic surface of the materials due to the presence of negatively charged POMs which makes them highly dispersed and stable in water. Using 1−3 as electrocatalysts, oxygen evolution reaction (OER) is studied under alkaline condition. For catalytic OER, 1−3 on the nickel foam (NF) electrode require almost 20 mV less overpotential compared to the undoped core material Mo x O y @FeO(OH) and the POM-free bare FeO(OH) and Ni x Fe 1−x O(OH). The better OER activity can be correlated to better electrokinetics, realized from the Tafel slope and charge-transfer resistance (R ct ). The fabricated electrode 1@NF not only shows a long-term stability under the OER condition but also can be fabricated to a watersplitting electrolyzer using a graphite rod as the cathode to produce green hydrogen with Faradaic efficiency of ca. 72%. In this study, Anderson-type POM is used as a potential ligand to derive the quantum-dot-sized Ni x Fe 1−x O(OH) core as a reactive electrocatalyst for OER. In a broad context, this strategy, i.e., the use of POM as a pure inorganic ligand to stabilize a reactive metal oxide nanocore, can further be adapted to design a variety of multimetallic or mixed-valence metal oxide materials.

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Section: Resultsmentioning

confidence: 99%

Section: Isolation Of Soluble Ni X Fe 1−x O(oh) Stabilized By [Mo 7 O...mentioning

confidence: 99%

Stabilization of Nickel-Doped Iron-oxy-hydroxide Core in Water by Heptamolybdate Ions to Improve the Electrochemical Oxygen Evolution Reaction

Samanta,

Mallick,

Chakraborty

2023

ACS Appl. Energy Mater.

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“…which would further impact the environmental fate of various metal ions and organic matters [ 18 , 19 , 20 , 21 ]. Studies have indicated that some iron oxides can act as natural photocatalysts to catalyze the oxidation of organic matters [ 22 , 23 , 24 ], and ferrihydrite could also act as a semiconductor material for Mn(II) oxidation [ 25 , 26 ] and organic matter degradation [ 23 ]. Hence, ferrihydrite is expected to show photocatalytic properties and induce redox reactions.…”

Section: Introductionmentioning

confidence: 99%

Light Promotes the Immobilization of U(VI) by Ferrihydrite

Wang

Ding

et al. 2022

Molecules

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The environmental behaviors of uranium closely depend on its interaction with natural minerals. Ferrihydrite widely distributed in nature is considered as one main natural media that is able to change the geochemical behaviors of various elements. However, the semiconductor properties of ferrihydrite and its impacts on the environmental fate of elements are sometimes ignored. The present study systematically clarified the photocatalysis of U(VI) on ferrihydrite under anaerobic and aerobic conditions, respectively. Ferrihydrite showed excellent photoelectric response. Under anaerobic conditions, U(VI) was converted to U(IV) by light-irradiated ferrihydrite, in the form of UO2+x (x < 0.25), where •O2− was the dominant reactive reductive species. At pH 5.0, ~50% of U(VI) was removed after light irradiation for 2 h, while 100% U(VI) was eliminated at pH 6.0. The presence of methanol accelerated the reduction of U(VI). Under aerobic conditions, the light illumination on ferrihydrite also led to an obvious but slower removal of U(VI). The removal of U(VI) increased from ~25% to 70% as the pH increased from 5.0 to 6.0. The generation of H2O2 under aerobic conditions led to the formation of UO4•xH2O precipitates on ferrihydrite. Therefore, it is proved that light irradiation on ferrihydrite significantly changed the species of U(VI) and promoted the removal of uranium both under anaerobic and aerobic conditions.

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“…[1][2][3][4][5][6][7][8][9] The process involves the reduction of water to hydrogen and the oxidation of water to oxygen. Because of their oxidative stability, metal oxides, such as BiVO 4 , 10,11 WO 3 , [12][13][14] and Fe 2 O 3 , [15][16][17][18] are preferred photoanode materials even though their electronic properties are inferior 19,20 to that of traditional semiconductors. Recently, CuWO 4 has gained interest as a water oxidation photoanode material because its smaller bandgap of 2.3 eV allows for better absorption of visible light, compared to WO 3 (2.6-2.8 eV) [21][22][23] or BiVO 4 (2.4 eV).…”

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confidence: 99%

Role of Surface States in Photocatalytic Oxygen Evolution with CuWO₄ Particles

Zhao

Cheung

et al. 2018

J. Electrochem. Soc.

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CuWO4 is a medium bandgap (2.3 eV) n-type semiconductor capable of photoelectrochemical water oxidation under applied electrical bias. Here, we show for the first time that suspended microcrystals CuWO4 evolve oxygen photocatalytically under visible illumination from solutions of 0.05 M AgNO3 (10.8 μmol/hour; AQE of 0.56% at 400 nm) and 0.0002 M FeCl3 (1.5 μmol/hour). No oxygen is detected with 0.002 M [Fe(CN)6]3− as sacrificial agent. The activity dependence on the redox potential of the acceptors is due to the presence of Cu2+ based electron trap states in CuWO4. According to surface photovoltage spectroscopy and electrochemistry, these states are located on the particle surface, 1.8 eV above the valence band edge of the material. Controlling the chemistry of these states will be key to uses of CuWO4 particles in tandem catalysts for overall water splitting.

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Photocatalytic water oxidation with iron oxide hydroxide (rust) nanoparticles

Cited by 8 publications

References 36 publications

Stabilization of Nickel-Doped Iron-oxy-hydroxide Core in Water by Heptamolybdate Ions to Improve the Electrochemical Oxygen Evolution Reaction

Stabilization of Nickel-Doped Iron-oxy-hydroxide Core in Water by Heptamolybdate Ions to Improve the Electrochemical Oxygen Evolution Reaction

Light Promotes the Immobilization of U(VI) by Ferrihydrite

Role of Surface States in Photocatalytic Oxygen Evolution with CuWO₄ Particles

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Photocatalytic water oxidation with iron oxide hydroxide (rust) nanoparticles

Cited by 8 publications

References 36 publications

Stabilization of Nickel-Doped Iron-oxy-hydroxide Core in Water by Heptamolybdate Ions to Improve the Electrochemical Oxygen Evolution Reaction

Stabilization of Nickel-Doped Iron-oxy-hydroxide Core in Water by Heptamolybdate Ions to Improve the Electrochemical Oxygen Evolution Reaction

Light Promotes the Immobilization of U(VI) by Ferrihydrite

Role of Surface States in Photocatalytic Oxygen Evolution with CuWO4 Particles

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Role of Surface States in Photocatalytic Oxygen Evolution with CuWO₄ Particles