Electrocatalytic water oxidation reaction promoted by cobalt-Prussian blue and its thermal decomposition product under mild conditions

Zambiazi, Priscilla J.; Aparecido, Gabriel de Oliveira; Ferraz, Thiago V. B.; Skinner, William S. J.; Yoshimura, Rafael G.; Moreira, Daniel E. B.; Germscheidt, Rafael L.; Nascimento, Lucas L.; Patrocínio, Antonio Otávio T.; Formiga, André Luiz Barboza; Bonacin, Juliano Alves

doi:10.1039/d0dt02220a

Cited by 15 publications

(31 citation statements)

References 52 publications

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“…To further confirm the preparation of crystal e-NiHCF and transformation of the amorphous structure, Raman spectroscopy was also carried out. As presented in Figure S4, the characteristic peaks, centered at 2086, 2120  , and 2143 cm –1 , could be assigned to the CN –1 stretching vibrations of e-NiHCF, − which were almost the same as those of a-NiHCF, indicating that there was no formation of new bonds during the activation process …”

Section: Results and Discussionmentioning

confidence: 94%

In Situ Synthesis of Superhydrophilic Amorphous NiFe Prussian Blue Analogues for the Oxygen Evolution Reaction at a High Current Density

Wang

et al. 2021

ACS Sustainable Chem. Eng.

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Synthesis of efficient and low-cost catalysts for the oxygen evolution reaction (OER) is a pivotal process for large-scale electrocatalytic water splitting to produce hydrogen. Prussian blue analogues (PBAs) prepared by the conventional co-precipitation method, with a less active site density and a poor electrical transport, are often used as precursors for further preparation of PBA derivatives, such as metal oxides, metal alloys, metal phosphides, and so on, due to their poor OER activity. In this report, controllable synthesis of NiFe PBA with Fe2O3 byproducts on a Ni foam substrate was achieved through a facile one-step hydrothermal reaction by adjusting the amount of urea and potassium ferricyanide. After chemical etching and electrochemical activation, NiFe PBA was entirely transformed into amorphous superhydrophilic NiFe PBA (denoted a-NiHCF), which exhibited a remarkable OER performance at a large current density. To drive high current densities of 400 and 800 mA cm–2, only ultralow overpotentials of 280 and 309 mV were required, respectively, which far exceed many recently reported OER catalysts. The superior performance can be attributed to the following: (1) in situ growth on a metal foam substrate can improve the structural stability and provide a faster charge transfer as well as oxygen bubble release; (2) chemical etching allows exposing more surface active sites; (3) an electrochemical activation-induced amorphous surface possesses a larger Brunauer–Emmett–Teller surface area, more high-valent oxidation states, and higher intrinsic OER activity; and (4) the superhydrophilic surface structure is conducive to the adsorption of water molecules. These advantages make a-NiHCF a promising candidate for application in the field of electrocatalytic water splitting.

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Section: Results and Discussionmentioning

confidence: 94%

In Situ Synthesis of Superhydrophilic Amorphous NiFe Prussian Blue Analogues for the Oxygen Evolution Reaction at a High Current Density

Wang

et al. 2021

ACS Sustainable Chem. Eng.

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“…In heterogeneous assemblies, the surface concentration of active catalytic sites is also an important parameter that governs catalytic activity. ,, The number of active catalytic cobalt sites is estimated by recording Co 2+/3+ redox wave at different scan rates (Figure S5). All dyad assemblies exhibit a relatively higher surface concentration compared to regular cobalt hexacyanoferrates due to the less crystalline nature of cobalt pentacyanoferrates. ,, [CoFe–CM] exhibits a surface concentration of 26 nmol cm –2 , which is around 25% higher than [CoFe–MB] (21 nmol cm –2 ) and 65% higher than [CoFe–SF] (16 nmol cm –2 ). This trend is also in good accordance with the Co/Fe atomic ratio obtained by EDX analysis.…”

Section: Resultsmentioning

confidence: 99%

“…All dyad assemblies exhibit a relatively higher surface concentration compared to regular cobalt hexacyanoferrates due to the less crystalline nature of cobalt pentacyanoferrates. 20,47,48 [CoFe−CM] exhibits a surface concentration of 26 nmol cm −2 , which is around 25% higher than [CoFe−MB] (21 nmol cm −2 ) and 65% higher than [CoFe−SF] (16 nmol cm −2 ). This trend is also in good accordance with the Co/Fe atomic ratio obtained by EDX analysis.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“Plug and Play” Photosensitizer–Catalyst Dyads for Water Oxidation

Oglou

Ghobadi

Özbay

et al. 2022

ACS Appl. Mater. Interfaces

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We present a simple and easy-to-scale synthetic method to plug common organic photosensitizers into a cyanide-based network structure for the development of photosensitizer-water oxidation catalyst (PS-WOC) dyad assemblies for the photocatalytic water oxidation process. Three photosensitizers, one of which absorbs red light similar to P680 in photosystem II, were utilized to harvest different regions of the solar spectrum. Photosensitizers are covalently coordinated to CoFe Prussian blue structures to prepare PS-WOC dyads. All dyads exhibit steady water oxidation catalytic activities throughout a 6 h photocatalytic experiment. Our results demonstrate that the covalent coordination between the PS and WOC group not only enhances the photocatalytic activity but also improves the robustness of the organic PS group. The photocatalytic activity of "plug and play" dyads relies on several structural and electronic parameters, including the position of the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the PS with respect to the HOMO level of the catalytic site, the intensity and wavelength of the absorption band of the PS, and the number of catalytic sites.

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“…1,2 Therefore, water splitting has been gaining attention in the past years, since it is the process of producing H 2 directly from water, via 2 half-reactions, known as the oxygen evolution reaction (OER) or water oxidation reaction (WOR) and the hydrogen evolution reaction (HER). 3,4 Although the overall process may seem simple, the WOR presents itself as the bottleneck reaction and requires a catalyst to be efficient. 5 Different classes of catalysts for WOR have been studied in the past years; however, noble metal catalysts are not viable in the long term.…”

Section: Introductionmentioning

confidence: 99%

“…Hydrogen is considered the most promising clean fuel for the future; however, its cleanness is directly related to the production pathway. , Therefore, water splitting has been gaining attention in the past years, since it is the process of producing H 2 directly from water, via 2 half-reactions, known as the oxygen evolution reaction (OER) or water oxidation reaction (WOR) and the hydrogen evolution reaction (HER). , Although the overall process may seem simple, the WOR presents itself as the bottleneck reaction and requires a catalyst to be efficient …”

Section: Introductionmentioning

confidence: 99%

Water Oxidation Performance Enhanced by Electrochemically Designed Vacancies on a Prussian Blue Catalyst

Germscheidt

Francischini

Silva

et al. 2022

ACS Appl. Energy Mater.

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Prussian blue analogues are one of the most promising examples of water oxidation catalysts presenting great performance, activity, and stability under mild conditions. Herein, we report an alternative methodology to synthesize the Prussian blue, obtaining a catalyst with vacancies created by an electrochemical method. This catalyst showed an outstanding activity, with an onset overpotential of 361 mV. Using pyridine as a molecular probe, we identified the presence of vacant Fe2+ sites, and the quantification of these sites allowed us to estimate a TOF number of 0.2170 s–1 for the water oxidation reaction. These results indicate that defect engineering is a versatile strategy to boost the catalytic activity in Prussian blue analogues by increasing the number of active sites.

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Electrocatalytic water oxidation reaction promoted by cobalt-Prussian blue and its thermal decomposition product under mild conditions

Abstract: Cobalt-Prussian blue analogues are remarkable catalysts for the oxygen evolution reaction (water oxidation) under mild conditions such as neutral pH. Although there is extensive reports on literature about the application...

Cited by 15 publications

References 52 publications

In Situ Synthesis of Superhydrophilic Amorphous NiFe Prussian Blue Analogues for the Oxygen Evolution Reaction at a High Current Density

In Situ Synthesis of Superhydrophilic Amorphous NiFe Prussian Blue Analogues for the Oxygen Evolution Reaction at a High Current Density

“Plug and Play” Photosensitizer–Catalyst Dyads for Water Oxidation

Water Oxidation Performance Enhanced by Electrochemically Designed Vacancies on a Prussian Blue Catalyst

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