Molecular and heterogeneous water oxidation catalysts: recent progress and joint perspectives

Li, Jingguo; Triana, Carlos A.; Wan, Wenchao; Saseendran, Devi Prasad Adiyeri; Zhao, Yonggui; Balaghi, S. Esmael; Heidari, Sima; Patzke, Greta R.

doi:10.1039/d0cs00978d

Cited by 132 publications

(139 citation statements)

References 387 publications

(513 reference statements)

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“…Massive efforts have thus been made to improve the OER performance of SACs, such as the regulation of coordination environments of the metal centers, interaction of diatomic metal sites, etc. 44 . Inspired by the recent development of NiFe coordination polymers for high OER performance 45 , we here developed the NiFe-CNG dual-site SACs with the goal of notably improving the OER performance of the above single-site SACs.…”

Section: Resultsmentioning

confidence: 99%

Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts

et al. 2021

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Single-atom catalysts with maximum metal utilization efficiency show great potential for sustainable catalytic applications and fundamental mechanistic studies. We here provide a convenient molecular tailoring strategy based on graphitic carbon nitride as support for the rational design of single-site and dual-site single-atom catalysts. Catalysts with single Fe sites exhibit impressive oxygen reduction reaction activity with a half-wave potential of 0.89 V vs. RHE. We find that the single Ni sites are favorable to promote the key structural reconstruction into bridging Ni-O-Fe bonds in dual-site NiFe SAC. Meanwhile, the newly formed Ni-O-Fe bonds create spin channels for electron transfer, resulting in a significant improvement of the oxygen evolution reaction activity with an overpotential of 270 mV at 10 mA cm−2. We further reveal that the water oxidation reaction follows a dual-site pathway through the deprotonation of *OH at both Ni and Fe sites, leading to the formation of bridging O2 atop the Ni-O-Fe sites.

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Section: Resultsmentioning

confidence: 99%

Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts

et al. 2021

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“…[ 6–8 ] Thanks to their unique atomic arrangement, these materials own structural flexibility and distinctively coordinated metal centers. [ 9–11 ] Electrochemically, amorphous oxides can be obtained by electrodeposition [ 12–14 ] or electrochemical restructuring [ 9,15–19 ] of crystalline materials. The latter approach has improved catalytic activity compared to their crystalline variant in some cases, [ 9,10,12,20 ] while this was not the case for other combinations of pristine materials and electrolytes.…”

Section: Introductionmentioning

confidence: 99%

Requirements for Beneficial Electrochemical Restructuring: A Model Study on a Cobalt Oxide in Selected Electrolytes

Villalobos

González-Flores

Urcuyo

et al. 2021

Advanced Energy Materials

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The requirements for beneficial materials restructuring into a higher performance oxygen evolution reaction (OER) electrocatalyst are still a largely open question. Here erythrite (Co3(AsO4)2·8H2O) is used as a Co‐based OER electrocatalyst to evaluate its catalytic properties during in situ restructuring into an amorphous Co‐based catalyst in four different electrolytes at pH 7. Using diffraction, microscopy, and spectroscopy, a strong effect in the restructuring behavior is observed depending of the anions in the electrolyte. Only carbonate electrolyte can activate the catalyst material, which is related to its slow restructuring process. While the catalyst turnover frequency (TOF) undesirably reduces by a factor of 28, the number of redox active sites continuously increases to a factor of 56, which results in an overall twofold increase in current of the restructured catalyst after 800 cycles. The activation is attributed to an adequate local order, a high Co oxidation state close to 3+, and a high number of redox‐active Co ions. These three requirements for beneficial restructuring provide new insights into the rational design of high‐performance OER catalysts by electrochemical restructuring.

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“…For example, the vacancy, point defects in bulk materials and surface, the exposed lattice facets, the bridge sites, terrace kinks, edge structures, and coordination, significantly influence the activity of the catalyst. Different from molecular water oxidation catalysts that are homogeneously dissolved in water, heterogeneous catalysts do not show abundant catalytic sites in a well-defined single crystalline surface or unique catalytic sites in a complex polycrystalline surface [12,13]. Such ambiguities greatly increase the difficulties in proposing a clear reaction mechanism, the lack of which has been a key reason for the sluggish progress in finding catalysts that can contribute to practical artificial photosynthesis.…”

Section: Introductionmentioning

confidence: 99%

“…It is noted that there have been some excellent reviews on the topic of water oxidation. They focus on, for example, materials [4,9], theoretical design [15,16], and overviews of the field [13,17]. Instead of replicating these efforts, we aim to center our discussions round the chemical mechanisms by which water is oxidized.…”

Section: Introductionmentioning

confidence: 99%

Mechanisms of water oxidation on heterogeneous catalyst surfaces

Yang

Wang

et al. 2021

Nano Res.

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Water oxidation, an essential step in photosynthesis, has attracted intense research attention. Understanding the reaction pathways at the electrocatalyst/water interface is of great importance for the development of water oxidation catalysts. How the water is oxidized on the electrocatalyst surface by the positive charges is still an open question. This review summarizes current advances in studies on surface chemistry within the context of water oxidation, including the intermediates, reaction mechanisms, and their influences on the reaction kinetics. The Tafel analyses of some electrocatalysts and the rate-laws relative to charge consumption rates are also presented. Moreover, how the multiple charge transfer relies on the intermediate coverage and the accumulated charge numbers is outlined. Lastly, the intermediates and rate-determining steps on some water oxidation catalysts are discussed based on density functional theories.

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Molecular and heterogeneous water oxidation catalysts: recent progress and joint perspectives

Abstract: The recent synthetic and mechanistic progress in molecular and heterogeneous water oxidation catalysts highlights the new, overarching strategies for knowledge transfer and unifying design concepts.

Cited by 132 publications

References 387 publications

Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts

Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts

Requirements for Beneficial Electrochemical Restructuring: A Model Study on a Cobalt Oxide in Selected Electrolytes

Mechanisms of water oxidation on heterogeneous catalyst surfaces

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