Cooperative electrochemical water oxidation by Zr nodes and Ni–porphyrin linkers of a PCN-224 MOF thin film

Usov, Pavel M.; Ahrenholtz, Spencer R.; Maza, William A.; Stratakes, Bethany M.; Epley, Charity C.; Kessinger, Matthew C.; Zhu, Jie; Morris, Amanda J.

doi:10.1039/c6ta05877a

Cited by 115 publications

(94 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[100] CPE in 0.1 m NaClO 4 at 1.5 Vv ersus NHE for 1h reveals O 2 production that is significantly greater than that observed for bare FTO and PCN-224-fb. The TOF was (2 AE 1) 10 À4 s À1 with aF Eo fa pproximately 30 %, which is consistent with the FE observed for Ni II TCPP in solution under the same conditions.…”

Section: Oermentioning

confidence: 65%

“…[100] The BET surfacea rea of PCN-224-Ni was 2600 m 2 g À1 .P CN-224-Ni thin films on fluorine-doped tin oxide (FTO) were synthesized by as olvothermalr eaction and were electrochemically investigated for the OER in 0.1 m NaClO 4 aqueous solutions. Ac urrent increase was observeda t 1.0 Vv ersus the normal hydrogen electrode (NHE) for PCN-224-Nit hat is much greatert han that observed forb are FTO and the free-base porphyrin MOF analogue,P CN-224-fb.…”

Section: Oermentioning

confidence: 99%

See 1 more Smart Citation

Electrocatalytic Metal–Organic Frameworks for Energy Applications

2017

View full text Add to dashboard Cite

With the global energy demand expected to increase drastically over the next several decades, the development of a sustainable energy system to meet this increase is paramount. Renewable energy sources can be coupled with electrochemical conversion processes to store energy in chemical bonds. To promote these difficult transformations, electrocatalysts that operate at high conversion rates and efficiency are required. Metal–organic frameworks (MOFs) have emerged as a promising class of materials; however, the insulating nature of MOFs has limited their application as electrocatalysts. The recent development of conductive MOFs has led to several electrocatalytic MOFs that display activity comparable to that of the best‐performing heterogeneous catalysts. Although many electrocatalytic MOFs exhibit low activity and stability, the few successful examples highlight the possibility of MOF electrocatalysts as replacements for noble‐metal‐based catalysts in commercial energy‐converting devices. We review herein the use of pristine MOFs as electrocatalysts to facilitate important energy‐related reactions.

show abstract

Section: Oermentioning

confidence: 65%

Section: Oermentioning

confidence: 99%

Electrocatalytic Metal–Organic Frameworks for Energy Applications

2017

View full text Add to dashboard Cite

show abstract

“…20–22 In this context, several groups have developed MOFs that show PCET behavior resulting in good photo- and electro-chemical activities. 22–24 PCET has been suggested to occur on the linker, 24 the node, 25 and the linker and node combined 22,23 but has not been studied in well-known photoactive MOFs. In this work, we provide an in-depth analysis of the PCET behavior in the widely used MIL-125.…”

Section: ■Introductionmentioning

confidence: 99%

Bulk-to-Surface Proton-Coupled Electron Transfer Reactivity of the Metal–Organic Framework MIL-125

et al. 2018

View full text Add to dashboard Cite

Stoichiometric proton-coupled electron transfer (PCET) reactions of the metal−organic framework (MOF) MIL-125, Ti8O8(OH)4(bdc)6 (bdc = terephthalate), are described. In the presence of UV light and 2-propanol, MIL-125 was photoreduced to a maximum of 2(e−/H+) per Ti8 node. This stoichiometry was shown by subsequent titration of the photoreduced material with the 2,4,6-tri-tert-butylphenoxyl radical. This reaction occurred by PCET to give the corresponding phenol and the original, oxidized MOF. The high level of charging, and the independence of charging amount with particle size of the MOF samples, shows that the MOF was photocharged throughout the bulk and not only at the surface. NMR studies showed that the product phenol is too large to fit in the pores, so the phenoxyl reaction must have occurred at the surface. Attempts to oxidize photoreduced MIL-125 with pure electron acceptors resulted in multiple products, underscoring the importance of removing e− and H+ together. Our results require that the e− and H+ stored within the MOF architecture must both be mobile to transfer to the surface for reaction. Analogous studies on the soluble cluster Ti8O8(OOCtBu)16 support the notion that reduction occurs at the Ti8 MOF nodes and furthermore that this reduction occurs via e−/H+ (H-atom) equivalents. The soluble cluster also suggests degradation pathways for the MOFs under extended irradiation. The methods described are a facile characterization technique to study redox-active materials and should be broadly applicable to, for example, porous materials like MOFs.

show abstract

“…An ideal catalyst must have good properties of high catalytic activity, good costeffectiveness, outstanding stability, a great number of exposed active sites, and high porosity for mass transport. [201] Copyright 2016, Royal Society of Chemistry. For example, some MOF Fe_MOF-525 with added trifluoroethanol (blue curve).…”

Section: Discussionmentioning

confidence: 99%

“…In order to address this problem, Usov et al successfully synthesized PCN-224-Ni (Figure 16c) containing Zr-oxo nodes and Ni(II)TCPP for electrochemical water oxidation, in which Zr 4 + preserves the structural stability. [201] The Ni(II)TCPP acts as the active catalytic sites, and the Zr nodes play a role as proton abstractors. The SEM image of PCN-224-Ni film is shown in Figure 16g.…”

Section: Zr/m Bimetallic-mof Catalystsmentioning

confidence: 99%

Pristine Transition‐Metal‐Based Metal‐Organic Frameworks for Electrocatalysis

Sun

Xue

et al. 2019

ChemElectroChem

View full text Add to dashboard Cite

Pristine metal‐organic frameworks (MOFs) and their composites, which have received wide attention in recent years, especially in the field of electrocatalysis, are emerging as distinctive electrocatalysts for the oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), oxygen evolution reaction (OER), and many other electrochemical redox reactions. In this review, the attention is focused on the development of monometallic‐MOFs and multimetallic‐MOFs (including bimetallic‐MOFs and trimetallic‐MOFs) for electrocatalysis in recent years, including their design, catalytic performance and strategies for activity improvement. Finally, major challenges in utilizing pristine MOFs and their composites for electrocatalysis are highlighted.

show abstract

Cooperative electrochemical water oxidation by Zr nodes and Ni–porphyrin linkers of a PCN-224 MOF thin film

Abstract: Here, we demonstrate a new strategy for cooperative catalysis and proton abstraction via the incorporation of independent species competent in the desired reactivity into a metal–organic framework (MOF) thin film.

Cited by 115 publications

References 49 publications

Electrocatalytic Metal–Organic Frameworks for Energy Applications

Electrocatalytic Metal–Organic Frameworks for Energy Applications

Bulk-to-Surface Proton-Coupled Electron Transfer Reactivity of the Metal–Organic Framework MIL-125

Pristine Transition‐Metal‐Based Metal‐Organic Frameworks for Electrocatalysis

Contact Info

Product

Resources

About