Boosting Electrocatalytic Oxygen Evolution by Cation Defect Modulation via Electrochemical Etching

Chen, Xiang; Yu, Meng; Yan, Zhenhua; Guo, Weiyi; Fan, Guilan; Ni, Youxuan; Liu, Jiuding; Zhang, Wei; Xie, Wei; Cheng, Peng; Chen, Jun

doi:10.31635/ccschem.020.202000194

Cited by 83 publications

(66 citation statements)

References 5 publications

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“…DFT calculation results revealed that the obtained nanomaterial with cationic vacancies could lower the energy barriers for intermediates and accelerate the release of generated O 2 . As a result, the designed electrocatalyst exhibited a small overpotential of 220 mV to deliver 20 mA cm −2 , and presented excellent long‐term stability at a current density of 40 mA cm −2 for more than 200 h. More recently, Cheng and co‐workers [ 41 ] created iron vacancies in FeNi 2 O 4 (FNO) via a facile electrochemical reduction etching strategy at room temperature (Figure 4b,c). Defective FNO (V Fe ‐FNO) was obtained at a constant potential of −0.58 V for 1500 s and Fe 3+ was reduced to Fe (0) as shown by the cyclic voltammetry (CV) profile.…”

Section: Classification Of Vacanciesmentioning

confidence: 99%

Recent Progress of Vacancy Engineering for Electrochemical Energy Conversion Related Applications

Zhao

Jin

et al. 2020

Adv Funct Materials

221

129

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Efficient electrocatalysts are key requirements for the development of ecofriendly electrochemical energy‐related technologies and devices. It is widely recognized that the introduction of vacancies is becoming an important and valid strategy to promote the electrocatalytic performances of the designed nanomaterials. In this review, the significance of vacancies (i.e., cationic vacancies, anionic vacancies, and mixed vacancies) on the improvement of electrocatalytic performances via three main functionalities, including tuning the electronic structure, regulating the active sites, and improving electrical conductivity, is systematically discussed. Recent achievements in vacancy engineering on various hotspot electrocatalytic processes are comprehensively summarized, with focus on the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), nitrogen reduction reaction (NRR), CO2 reduction reaction (CO2RR), and their further applications in overall water‐splitting and zinc–air battery devices. The recent development of vacancy engineering for other energy‐related applications is also summarized. Finally, the challenges and prospects of vacancy engineering to regulate the electrocatalytic performances of different electrochemical reactions are discussed.

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Section: Classification Of Vacanciesmentioning

confidence: 99%

Recent Progress of Vacancy Engineering for Electrochemical Energy Conversion Related Applications

Zhao

Jin

et al. 2020

Adv Funct Materials

221

129

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“…Compared with the creation of anion defects in transition metal‐based composites, the higher formation energy makes it more challenging to controllably produce cation vacancies in metal compounds. The methods used to create cation defects in metal complexes include in situ formation, [ 93–96 ] thermal calcination, [ 19,97 ] chemical/electrochemical etching, [ 98–100 ] and plasma treatment. [ 75,101,102 ] In this section, the influence of single type of cation defects such as Co, Fe, and Ni vacancies and multivacancies such as oxygen, Fe, and Co vacancies on the electrochemical reactions will be discussed.…”

Section: Cation Defects In Transition Metal Composites For Electrocatmentioning

confidence: 99%

“…For example, the synthesis of spinel‐type FeNi 2 O 4 (FNO) with adjustable density of Fe defects (V Fe ‐FNO) is realized by an electrochemical reduction etching method. [ 98 ] The defective FNO with different concentrations of Fe vacancies can be fabricated through altering the cathodic potential or tuning the etching time (Figure 11d). The produced reactive Fe species during the cathodic reaction can be etched in 1.0 m KOH (Figure 11e), [ 107 ] thereby Fe defects are created in the spinel iron nickel oxide.…”

Section: Cation Defects In Transition Metal Composites For Electrocatmentioning

confidence: 99%

Defective Structures in Metal Compounds for Energy‐Related Electrocatalysis

2020

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Catalysts play a critical role in accelerating the electrochemical reactions. Engineering the electronic structures and surface properties of electrocatalysts is a feasible approach to improve their catalytic performance. Introducing defects such as anion and cation vacancies into transition metal‐based materials to enhance their activity for various energy‐related electrocatalytic reactions has been receiving increasingly attention in recent years. In this review, a systematic summary of the anion and cation defects on different electrochemical reactions will be presented. In particular, the commonly used methods to produce anion vacancies (such as oxygen, sulfur, and phosphorus defects) and cation vacancies (such as Fe, Co, and Ni defects) will be discussed. The control of the defect density and refilling heteroatoms to stabilize the anion defects and simultaneously to further enhance their catalytic performance are also summarized. In addition, recent work on creating multivacancies in transition metal‐based electrocatalysts for maximizing their catalytic activities is reviewed as well. Finally, future research on defect engineering in metal compounds for electrocatalysis is proposed. This review will guide the further development of various energy‐related electrocatalytic reactions promoted by defective structures in metal composites.

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“…Electrochemical water splitting, including hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), holds great potentials as a promising technology for the sustainable storage, conversion, and transportation of hydrogen energy and it strongly depends on the thermodynamics and kinetics parameters of its two half reactions. [1][2][3] Taking sustainability of H production into consideration, seawater electrolysis is an eminently desirable path owing to its earth-abundant reserves account for 96.5% of the world's total water resources. Although Pt-based and Ru/Ir-based electrocatalysts are recognized to be effective in reducing reaction energy barrier and boosting seawater splitting efficiency, the limited earth-abundance and expensive market-price severely hamper their extensive applications.…”

Section: Introductionmentioning

confidence: 99%

Ultrathin Metal–Organic Framework Nanosheets-Derived Yolk–Shell Ni _0.85 Se@NC with Rich Se-Vacancies for Enhanced Water Electrolysis

et al. 2021

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Selecting ultrathin MOF nanosheets as pre-assembling platforms, yolk-shell structured few-layer N-doped carbon (NC) shell encapsulated Ni 0.85 Se core (denoted as Ni 0.85 Se@NC) via an oriented phase modulation (OPM) strategy are controllably fabricated. The ultrathin nature of MOF nanosheets give rise to the modification of structure at the electronic level with abundant Se-vacancies and effective electronic coupling via the Ni-N x coordination at the interface between the Ni 0.85 Se core and NC shell. The obtained Ni 0.85 Se@NC exhibits low overpotentials for both oxygen evolution reaction (OER) (300 mV) and hydrogen evolution reaction (HER) (157 mV) at 10 mA•cm-2 in alkaline condition, outperforming the corresponding bulk MOFderived counterparts. Through exploiting Ni 0.85 Se@NC as anode and cathode catalysts, a low cell voltage of 1.61 V is achieved to perform alkaline water electrolysis. Remarkably, it also achieves high activity in natural seawater (pH = 7.98) and simulated seawater (pH = 7.86) electrolytes, even surpassing integrated Pt/C-RuO 2 /CC electrodes. Density functional theory (DFT) studies illustrate that abundant Se-vacancies effectively regulate the electronic structure of Ni 0.85 Se@NC by accelerating electron transfer from Ni to N atoms at the interface, and thus make the Ni 0.85 Se@NC a near-optimal electronic configuration to stimulate ideal adsorption free energy toward key reaction intermediates.

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Boosting Electrocatalytic Oxygen Evolution by Cation Defect Modulation via Electrochemical Etching

Cited by 83 publications

References 5 publications

Recent Progress of Vacancy Engineering for Electrochemical Energy Conversion Related Applications

Recent Progress of Vacancy Engineering for Electrochemical Energy Conversion Related Applications

Defective Structures in Metal Compounds for Energy‐Related Electrocatalysis

Ultrathin Metal–Organic Framework Nanosheets-Derived Yolk–Shell Ni _0.85 Se@NC with Rich Se-Vacancies for Enhanced Water Electrolysis

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Boosting Electrocatalytic Oxygen Evolution by Cation Defect Modulation via Electrochemical Etching

Cited by 83 publications

References 5 publications

Recent Progress of Vacancy Engineering for Electrochemical Energy Conversion Related Applications

Recent Progress of Vacancy Engineering for Electrochemical Energy Conversion Related Applications

Defective Structures in Metal Compounds for Energy‐Related Electrocatalysis

Ultrathin Metal–Organic Framework Nanosheets-Derived Yolk–Shell Ni 0.85 Se@NC with Rich Se-Vacancies for Enhanced Water Electrolysis

Contact Info

Product

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Ultrathin Metal–Organic Framework Nanosheets-Derived Yolk–Shell Ni _0.85 Se@NC with Rich Se-Vacancies for Enhanced Water Electrolysis