Metal–Organic Framework Templated Pd@PdO–Co<sub>3</sub>O<sub>4</sub> Nanocubes as an Efficient Bifunctional Oxygen Electrocatalyst

Li, Hongchao; Zhang, Yingjie; Hu, Xiao; Liu, Wu‐Jun; Chen, Jie‐Jie; Yu, Han‐Qing

doi:10.1002/aenm.201702734

Cited by 101 publications

(59 citation statements)

References 41 publications

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“…The electrochemical active surface area (ECSA) plays a significant role in the OER catalytic ability, while the double‐layer capacitance ( C dl ) is proportional to the ECSA of catalysts. Therefore, C dl of HHTP@ZIF‐67 and ZIF‐67 were measured via cyclic voltammetry at different scan rates in the non‐faradaic region, in which no redox progress would occur. As presented in Figure S9 (Supporting Information), the C dl value of HHTP@ZIF‐67 is 56.43 mF cm −2 , nearly one time larger than that of pure ZIF‐67 (32.08 mF cm −2 ).…”

Section: Methodsmentioning

confidence: 99%

π‐Conjugated Molecule Boosts Metal–Organic Frameworks as Efficient Oxygen Evolution Reaction Catalysts

Zhu

Ding

et al. 2018

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102

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Metal-organic frameworks (MOFs), as a new type of promising materials in electrochemistry, are well investigated by researchers in recent years. [17][18][19][20] Due to the poor conductivity of MOFs, strategies are developed to increase the conductivity and improve the electrochemical performance, such as doping different elements (both metals and nonmetals), [21,22] incorporating conductive materials (such as graphene), [23,24] encapsulating active molecules, [25,26] and even undergoing calcination [27,28] or pyrolysis. [29][30][31] Zeolitic imidazolate frameworks (ZIFs), [32,33] as a new subfamily of MOFs, exhibit not only crystalline multiporosity as MOFs but also high thermal and chemical stability as zeolites. Attributed to the outstanding properties, ZIF derivatives are unique potential candidates in diversified applications such as chemical separation, [34,35] sensors, [36][37][38] energy storage, [39,40] and catalysis. [41,42] π-Conjugated molecules are used to construct planar conductive MOFs in recent years due to the high charge mobility and the corresponding MOFs are explored as good electrocatalysts, [43] electrode materials, [44] sensors, [45] and so on. In our study, a simple MOF architecture, named ZIF-67, was used as the raw material to prepare a high-performance catalyst for OER. The organic molecule HHTP (2,3,6,7,10,11-hexahydroxytriphenylene) was coated on ZIF-67 via a facile one-step hydrothermal method and the obtained composite, denoted as HHTP@ZIF-67, presented higher electrocatalytic efficiency and durability than many reported MOF materials. To the best of our knowledge, this is the first time that a π-conjugated molecule was coated directly on MOFs to ameliorate their electrochemical capabilities. This work will shed light on the further application of MOFs as promising electrocatalysts in energy storage and conversion.ZIF-67 was synthesized according to the previous work by Dong and co-workers [46] and utilized to prepare our porous electrocatalysts. The composite HHTP@ZIF-67 was successfully obtained after combining ZIF-67 together with HHTP under different solvothermal conditions (40, 60, 80, and 100 °C). The synthesis route is presented in Scheme 1.Since the as-prepared sample under 60 °C manifests the most uniform in both size and surface morphology that can be visualized in Figure S1 (Supporting Information), the following characterizations and discussions are focused on HHTP@ZIF-67 obtained under 60 °C when comparing with the pristine ZIF-67.To improve the efficiency of water electrolysis, developing efficient oxygen evolution reaction (OER) electrocatalysis is extremely important due to its four-electron transfer dynamics. In this work, a π-conjugated molecule (2,3,6,7,10,11-hexahydroxytriphenylene, HHTP), which can accelerate the electron transfer, is coated directly on pristine ZIF-67, resulting in a composite named HHTP@ZIF-67, via a simple one-step solvothermal method. The obtained HHTP@ZIF-67 possesses a Brunauer-Emmett-Teller surface area of 2013.9 m 2 g −1 and displays m...

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Section: Methodsmentioning

confidence: 99%

π‐Conjugated Molecule Boosts Metal–Organic Frameworks as Efficient Oxygen Evolution Reaction Catalysts

Zhu

Ding

et al. 2018

Small

102

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“…[12][13][14] In electrocatalysis, MOFs were used as precursors and/or sacrificial templates to prepare various electrocatalysts including metal oxides, phosphides, and sulfides supported on porous carbon through pyrolysis under different conditions. [15][16][17][18] However, the pyrolysis process completely destroys the intriguing structural and compositional properties of the precursors, and results in limited active sites and hindered reactant transport. To take full advantage of the unique properties of MOFs, it is reasonable to directly use them as (pre)electrocatalysts.…”

Section: Introductionmentioning

confidence: 99%

Strong Electronic Interaction Enhanced Electrocatalysis of Metal Sulfide Clusters Embedded Metal–Organic Framework Ultrathin Nanosheets toward Highly Efficient Overall Water Splitting

Zhao

et al. 2020

Advanced Science

143

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Unique metal sulfide (MS) clusters embedded ultrathin nanosheets of Fe/Ni metal-organic framework (MOF) are grown on nickel foam (NiFe-MS/MOF@NF) as a highly efficient bifunctional electrocatalyst for overall water splitting. It exhibits remarkable catalytic activity and stability toward both the oxygen evolution reaction (OER, ƞ = 230 mV at 50 mA cm −2) and hydrogen evolution reaction (HER, ƞ = 156 mV at 50 mA cm −2) in alkaline media, and bi-functionally catalyzes overall alkaline water splitting at a current density of 50 mA cm −2 by 1.74 V cell voltage without iR compensation. The enhancement mechanism is ascribed to the impregnated metal sulfide clusters in the nanosheets, which not only promote the formation of ultrathin nanosheet to greatly enlarge the reaction surface area while offering high electric conductivity, but more importantly, efficiently modulate the electronic structure of the catalytically active atom sites to an electron-rich state via strong electronic interaction and strengthen the adsorption of oxygenate intermediate to facilitate fast electrochemical reactions. This work reports a highly efficient HER/OER bifunctional electrocatalyst and may shed light on the rational design and synthesis of uniquely structured MOF-derived catalysts.

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“…. ARTICLES (Table S1) [27,33,[41][42][43][44][45][46][47][48][49][50][51][52][53][54][55]. The results indicated that the VO-rich Co 2 AlO 4 possessed a high OER kinetics.…”

Section: Methodsmentioning

confidence: 96%

Synthesis of ultrathin Co2AlO4 nanosheets with oxygen vacancies for enhanced electrocatalytic oxygen evolution

et al. 2019

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In this work, we reported the synthesis of twodimensional spinel structure of ultrathin Co 2 AlO 4 nanosheets via dealloying and subsequent annealing processes. Oxygen vacancy defects were further introduced into Co 2 AlO 4 nanosheets by a mild solvothermal reduction method, resulting in large electrochemical surface area and high active site densities, making the related Co atoms get electrons, and producing more empty orbitals. The positive charge of Co and Al atoms adjacent to the O vacancies in VO-rich Co 2 AlO 4 reduced significantly, that is, more electrons are concentrated on the Co and Al atoms. Those electrons closed to the Fermi level have a promoting effect during the H 2 O activation. As a result, the obtained ultrathin Co 2 AlO 4 nanosheets with oxygen vacancies show a low overpotential of 280 mV at the current density of 10 mA cm −2 and a small Tafel slope of 70.98 mV dec −1 . Moreover, it also displays a remarkable stability in alkaline solution, which is superior to most of the reported Co 3 O 4 electrocatalysts. The present work paves a new way to achieve efficient new energetic materials for sustainable community.

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Metal–Organic Framework Templated Pd@PdO–Co₃O₄ Nanocubes as an Efficient Bifunctional Oxygen Electrocatalyst

Cited by 101 publications

References 41 publications

π‐Conjugated Molecule Boosts Metal–Organic Frameworks as Efficient Oxygen Evolution Reaction Catalysts

π‐Conjugated Molecule Boosts Metal–Organic Frameworks as Efficient Oxygen Evolution Reaction Catalysts

Strong Electronic Interaction Enhanced Electrocatalysis of Metal Sulfide Clusters Embedded Metal–Organic Framework Ultrathin Nanosheets toward Highly Efficient Overall Water Splitting

Synthesis of ultrathin Co2AlO4 nanosheets with oxygen vacancies for enhanced electrocatalytic oxygen evolution

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Metal–Organic Framework Templated Pd@PdO–Co3O4 Nanocubes as an Efficient Bifunctional Oxygen Electrocatalyst

Cited by 101 publications

References 41 publications

π‐Conjugated Molecule Boosts Metal–Organic Frameworks as Efficient Oxygen Evolution Reaction Catalysts

π‐Conjugated Molecule Boosts Metal–Organic Frameworks as Efficient Oxygen Evolution Reaction Catalysts

Strong Electronic Interaction Enhanced Electrocatalysis of Metal Sulfide Clusters Embedded Metal–Organic Framework Ultrathin Nanosheets toward Highly Efficient Overall Water Splitting

Synthesis of ultrathin Co2AlO4 nanosheets with oxygen vacancies for enhanced electrocatalytic oxygen evolution

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Metal–Organic Framework Templated Pd@PdO–Co₃O₄ Nanocubes as an Efficient Bifunctional Oxygen Electrocatalyst