Zinc–cobalt oxides as efficient water oxidation catalysts: the promotion effect of ZnO

Feng, Rong; Zhao, Jiao; Su, Panpan; Yao, Yi; Li, Mingrun; Yang, Qihua; Li, Can

doi:10.1039/c4ta06527a

Cited by 59 publications

(32 citation statements)

References 43 publications

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“…surface area and morphology, is known to be very critical for WOCs as well. [56][57][58][59] Herein, we report M x Co 3−x O 4 (M = Co, Mn, Fe) porous nanocages with porous shells containing small nanoparticles by nonequilibrium interdiffusion (the Kirkendall effect) of Prussian blue analogue (PBA) M 3 [Co(CN) 6 ] 2 (M = Co, Mn, Fe) as efficient WOCs. 30,[53][54][55] However, due to the high surface energies, the traditional nano materials would agglomerate easily during the catalytic process, resulting in the decline of catalytic activity.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, Mg, Mn, Fe and Zn substituted Co 3 O 4 catalysts can improve the activity toward the water oxidation reaction. [56][57][58][59] Herein, we report M x Co 3Àx O 4 (M ¼ Co, Mn, Fe) porous nanocages with porous shells containing small nanoparticles by nonequilibrium interdiffusion (the Kirkendall effect) of Prussian blue analogues (PBAs) M 3 [Co(CN) 6 ] 2 (M ¼ Co, Mn, Fe) as efficient WOCs. PBAs are a class of crystalline metalorganic frameworks (MOFs) constructed from divalent and trivalent metal ions bridged by cyanide ligands (Fig.…”

Section: Introductionmentioning

confidence: 99%

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M_xCo_3−xO₄ (M = Co, Mn, Fe) porous nanocages derived from metal–organic frameworks as efficient water oxidation catalysts

et al. 2015

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The design and development of efficient and robust water oxidation catalysts based on earth-abundant elements are crucial for energy conversion and storage technology. Herein, we report Co3O4 porous nanocages derived from simple metal-organic frameworks by a simple self-assemble method and a low temperature anneal process. This method can synthesize MxCo3−xO4 (M = Co, Mn, Fe) porous nanocages materials and allow precise control of ratio of substituted metal in Co3O4 catalysts. These catalysts were investigated for photochemical, chemical-driven (cerium (IV)-driven) and electrochemical water oxidation, and they presented a superior activity for water oxidation. The high turnover frequency (TOF) of ∼3.2 × 10 -4 s -1 per Co atom was obtained under neutral pH using Co3O4 porous nanocages in photocatalytic water oxidation reaction, which is comparable with those of nanostructured Co3O4 clusters supported on mesoporous silica. Under cerium (IV)-driven water oxidation condition, a high TOF of ∼3.6 × 10 −3 s −1 per Co atom was achieved, which was the highest among those of other known reported cobalt oxides. The overpotential of Co3O4 porous nanocages for the electrochemical water oxidation (η = 0.42 V at 1 mA cm -2 ) is comparable to the reported overpotentials of catalysts based on cobalt. Multiple experimental results (e.g. XRD, TEM, HR-TEM and XPS) confirm that Co3O4 porous nanocages are highly stable. This study illustrates a guideline to the design and synthesis of inexpensive and highly active spinel catalysts for water oxidation. 6,40-46 Figure 1. Schematic representation of (a) polyhedral representation of Co 3 O 4 (b) ball-and-stick representation of Co 3 O 4 (c) ball-and-stick representation of Co 4 O 4 core in spinel Co 3 O 4 (d) Mn 4 CaO 5 in the photosystemⅡ-WOC. Turquoise: Co 3+ ; teal: Co 2+ ; red: O; violet: Mn; brown: Ca.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

M_xCo_3−xO₄ (M = Co, Mn, Fe) porous nanocages derived from metal–organic frameworks as efficient water oxidation catalysts

et al. 2015

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“…The octahedral coordination has a lower intensity at peak I than the tetrahedron one, as well as a higher intensity at peak III in Figure 4A. These imply that some Co 2+ cations in the lattice of crystal Co 3 O 4 are replaced by Zn 2+ cations (Rong et al., 2015) (Figure S14). The Zn K-edge XANES spectrum of Zn 0.2 :Co 1 @Cu appears as an absorption edge energy at 9,668.9 eV that is typical characteristics of Zn 2+ .…”

Section: Resultsmentioning

confidence: 94%

Photoelectrocatalytic Reduction of CO2 to Paraffin Using p-n Heterojunctions

Wang

Guan

et al. 2020

iScience

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Nowadays, photoelectrocatalytic (PEC) reduction of CO 2 represents a very promising solution for storing solar energy in value-added chemicals, but so far it has been hampered by the lack of highly efficient catalyst of photocathode. Enlightened by the Calvin cycle of plants, here we show that a series of three-dimensional C/N-doped heterojunctions of Zn x :Co y @Cu are successfully fabricated and applied as photocathodes in the PEC reduction of CO 2 to generate paraffin product. These materials integrate semiconductors of p-type Co 3 O 4 and n-type ZnO on Cu foam to construct fine heterojunctions with multiple active sites, which result in excellent CC coupling control in reduction of CO 2. The best catalyst of Zn 0.2 :Co 1 @Cu yields paraffin at a rate of 325 mg$h À1 under À0.4 V versus saturated calomel electrode without H 2 release. The apparent quantum efficiency of PEC cell is up to 1.95%.

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“…[10] However, it has low conductivity and stability [15,16] and unlike CoOOH/NiOOH, ZnOOH has little to no OER activity. [17][18][19] Obviously, these factors limit it potential as an electrode material for OER electrocatalysis. It therefore comes as no surprise that so far only two ZnFe 2 O 4 OER catalysts have been reported, [5,20] each with an average performance much lower than catalyst based on Co, Ni and RuO 2 .…”

Section: Introductionmentioning

confidence: 99%

In Situ Electrochemical Formation of a Core‐Shell ZnFe₂O₄@Zn(Fe)OOH Heterostructural Catalyst for Efficient Water Oxidation in Alkaline Medium

2020

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Low‐cost, stable and highly active electrocatalysts for the oxygen evolution reaction (OER) are needed to improve the efficiency of hydrogen production via water splitting. However, developing such a catalyst is still a challenge. Zinc ferrite (ZnFe2O4) is non‐toxic and made from cheap and earth‐abundant materials making it a potential raw material for synthesizing “green” low‐cost catalysts for the OER. However, it has largely been ignored due to its low stability, conductivity and OER‐inactive Zn2+. Herein, ZnFe2O4 is used effectively as a pre‐catalyst to synthesize core‐shell ZnFe2O4@Zn(Fe)OOH polycrystalline heterostructures in situ via cyclic voltammetry. The ZnFe2O4@Zn(Fe)OOH heterostructures display much higher OER catalytic activity and stability than the benchmark RuO2 catalyst in alkaline medium, owing to its high conductivity, stability and electrochemically active surface area (ECSA). Our findings thus reveal a new and effective way by which ZnFe2O4 can be applied in water electrolysis.

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Zinc–cobalt oxides as efficient water oxidation catalysts: the promotion effect of ZnO

Abstract: ZnO and Co3O4 in the interface of zinc–cobalt oxides work in a cooperative way as a water adsorption site and water oxidation site, respectively.

Cited by 59 publications

References 43 publications

M_xCo_3−xO₄ (M = Co, Mn, Fe) porous nanocages derived from metal–organic frameworks as efficient water oxidation catalysts

M_xCo_3−xO₄ (M = Co, Mn, Fe) porous nanocages derived from metal–organic frameworks as efficient water oxidation catalysts

Photoelectrocatalytic Reduction of CO2 to Paraffin Using p-n Heterojunctions

In Situ Electrochemical Formation of a Core‐Shell ZnFe₂O₄@Zn(Fe)OOH Heterostructural Catalyst for Efficient Water Oxidation in Alkaline Medium

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Zinc–cobalt oxides as efficient water oxidation catalysts: the promotion effect of ZnO

Abstract: ZnO and Co3O4 in the interface of zinc–cobalt oxides work in a cooperative way as a water adsorption site and water oxidation site, respectively.

Cited by 59 publications

References 43 publications

MxCo3−xO4 (M = Co, Mn, Fe) porous nanocages derived from metal–organic frameworks as efficient water oxidation catalysts

MxCo3−xO4 (M = Co, Mn, Fe) porous nanocages derived from metal–organic frameworks as efficient water oxidation catalysts

Photoelectrocatalytic Reduction of CO2 to Paraffin Using p-n Heterojunctions

In Situ Electrochemical Formation of a Core‐Shell ZnFe2O4@Zn(Fe)OOH Heterostructural Catalyst for Efficient Water Oxidation in Alkaline Medium

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Product

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M_xCo_3−xO₄ (M = Co, Mn, Fe) porous nanocages derived from metal–organic frameworks as efficient water oxidation catalysts

M_xCo_3−xO₄ (M = Co, Mn, Fe) porous nanocages derived from metal–organic frameworks as efficient water oxidation catalysts

In Situ Electrochemical Formation of a Core‐Shell ZnFe₂O₄@Zn(Fe)OOH Heterostructural Catalyst for Efficient Water Oxidation in Alkaline Medium