Advances in Understanding the Electrocatalytic Reconstruction Chemistry of Coordination Compounds

Liu, Xiong; Guo, Rui; Huang, Wenzhong; Zhu, Jiexin; Wen, Bo; Mai, Liqiang

doi:10.1002/smll.202100629

Cited by 12 publications

(10 citation statements)

References 209 publications

(230 reference statements)

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“…We kindly refer readers to recent representative reviews and research publications. 28,29,262,285,393,395,680 The combination of the obtained time-resolved information (sections 4.2 and 4.3) with those mentioned design principles (section 6.1.1) will contribute to the development of efficient and robust OER catalysts and pave the way to a carbon-neutral society.…”

Section: ) Leaves the Following Question Open: Do The Oxidized Anioni...mentioning

confidence: 99%

Oxygen Evolution/Reduction Reaction Catalysts: From In Situ Monitoring and Reaction Mechanisms to Rational Design

et al. 2023

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The oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are core steps of various energy conversion and storage systems. However, their sluggish reaction kinetics, i.e., the demanding multielectron transfer processes, still render OER/ORR catalysts less efficient for practical applications. Moreover, the complexity of the catalyst–electrolyte interface makes a comprehensive understanding of the intrinsic OER/ORR mechanisms challenging. Fortunately, recent advances of in situ/operando characterization techniques have facilitated the kinetic monitoring of catalysts under reaction conditions. Here we provide selected highlights of recent in situ/operando mechanistic studies of OER/ORR catalysts with the main emphasis placed on heterogeneous systems (primarily discussing first-row transition metals which operate under basic conditions), followed by a brief outlook on molecular catalysts. Key sections in this review are focused on determination of the true active species, identification of the active sites, and monitoring of the reactive intermediates. For in-depth insights into the above factors, a short overview of the metrics for accurate characterizations of OER/ORR catalysts is provided. A combination of the obtained time-resolved reaction information and reliable activity data will then guide the rational design of new catalysts. Strategies such as optimizing the restructuring process as well as overcoming the adsorption-energy scaling relations will be discussed. Finally, pending current challenges and prospects toward the understanding and development of efficient heterogeneous catalysts and selected homogeneous catalysts are presented.

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Section: ) Leaves the Following Question Open: Do The Oxidized Anioni...mentioning

confidence: 99%

Oxygen Evolution/Reduction Reaction Catalysts: From In Situ Monitoring and Reaction Mechanisms to Rational Design

et al. 2023

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“…Metal–organic frameworks (MOFs) with structural diversity, tunability and functionality have been utilized in varied fields − including electrochemical energy conversion. − The electrochemical conversion mainly depends on redox-active metal nodes, redox-active linkers, and/or host–guest redox activation . Particularly, in the field of electrochemical CO 2 reduction reaction (CO 2 RR), MOFs exhibit unique advantages not only because of their well dispersed metal centers with redox activity for CO 2 electroreduction, − but also owing to their tunable porosity to enhance adsorption of CO 2 making electron transfer easier from active site to CO 2 molecules. , Moreover, MOFs with atomically dispersed metal sites provide a potential platform for design and application of single-site catalysts. − For example, two-dimensional (2D) Cu-MOF with copper nodes as single active sites realized CO 2 RR to give CO through the fast reversible change between Cu 2+ and Cu + .…”

Section: Introductionmentioning

confidence: 99%

Copper(II) Frameworks with Varied Active Site Distribution for Modulating Selectivity of Carbon Dioxide Electroreduction

Yan

Wang

et al. 2022

ACS Appl. Mater. Interfaces

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Metal−organic frameworks (MOFs) can be utilized as electrocatalysts for CO 2 reduction reaction (CO 2 RR) due to their well dispersed metal centers. However, the influence of metal node distribution on electrochemical CO 2 RR was rarely explored. Here, three Cu-MOFs with different copper(II) site distribution were employed for CO 2 electroreduction. The Cu-MOFs Cu3) were achieved by using the same ligand 1,3,5-tris(1-imidazolyl)benzene (L) but different Cu(II) salts. The results show that the Faraday efficiency of CO (FE CO ) for Cu1 is 4 times that of the FE H2 , while the FE CO of Cu2 is twice that of the FE H2 . As for Cu3, there is not much difference between FE CO and FE H2 . Such difference may arise from the distinct electrochemical active surface area and charge transfer kinetics caused by different copper site distribution. Furthermore, the different framework structures also affect the activity of the copper sites, which was supported by the theoretically calculated Gibbs free energy and electron density, contributing to the selectivity of CO 2 RR. This study provides a strategy for modulating the selectivity of CO 2 RR by tuning the distribution of the active centers in MOFs.

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“…The first studies of MOFs considered them true catalysts for the OER . However, similar to many molecular systems, − the degradation or removal of organic fragments causes the decomposition of the molecular catalysts to metal (hydr)oxides after the OER. ,− On the other hand, metal (hydr)oxides (Mn, Fe, Co, Ni, and Cu) are efficient catalysts for the OER. Among different metal (hydr)oxides, Ni–Fe layered double hydroxide (LDH) are efficient OER catalysts.…”

Section: Introductionmentioning

confidence: 99%

“…In 2018, the study by Zhang’s group indicated that Ni–Fe Prussian blue analogue transformed to an Fe–Ni layered double hydroxide during the OER . Recently, the conversion of MOFs to metal (hydr)oxides under the OER was investigated by some research groups. − Although previous studies have pointed to the conversion of some MOFs to metal (hydr)oxides, the details of this conversion are unknown.…”

Section: Introductionmentioning

confidence: 99%

Further Insight into the Conversion of a Ni–Fe Metal–Organic Framework during Water-Oxidation Reaction

et al. 2022

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Metal–organic frameworks (MOFs) are extensively investigated as catalysts in the oxygen-evolution reaction (OER). A Ni–Fe MOF with 2,5-dihydroxy terephthalate as a linker has been claimed to be among the most efficient catalysts for the oxygen-evolution reaction (OER) under alkaline conditions. Herein, the MOF stability under the OER was reinvestigated by electrochemical methods, X-ray diffraction, X-ray absorption spectroscopy, energy-dispersive spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy, nuclear magnetic resonance, operando visible spectroscopy, electrospray ionization mass spectroscopy, and Raman spectroscopy. The peaks corresponding to the carboxylate group are observed at 1420 and 1520 cm–1 using Raman spectroscopy. The peaks disappear after the reaction, suggesting the removal of the carboxylate group. A drop in carbon content but growth in oxygen content after the OER was detected by energy-dispersive spectra. This shows that after the OER, the surface of MOF is oxidized. SEM images also show deep restructures in the surface morphology of this Ni–Fe MOF after the OER. Nuclear magnetic resonance and electrospray ionization mass spectrometry show the decomposition of the linker in alkaline conditions and even in the absence of potential. These experimental data indicate that during the OER, the synthesized MOF transforms to a Fe–Ni-layered double hydroxide, and the formed metal oxide is a candidate for the OER catalysis. Generalization is not true; however, taken together, these findings suggest that the stability of Ni–Fe MOFs under harsh oxidation conditions should be reconsidered.

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Advances in Understanding the Electrocatalytic Reconstruction Chemistry of Coordination Compounds

Cited by 12 publications

References 209 publications

Oxygen Evolution/Reduction Reaction Catalysts: From In Situ Monitoring and Reaction Mechanisms to Rational Design

Oxygen Evolution/Reduction Reaction Catalysts: From In Situ Monitoring and Reaction Mechanisms to Rational Design

Copper(II) Frameworks with Varied Active Site Distribution for Modulating Selectivity of Carbon Dioxide Electroreduction

Further Insight into the Conversion of a Ni–Fe Metal–Organic Framework during Water-Oxidation Reaction

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