A Lattice‐Oxygen‐Involved Reaction Pathway to Boost Urea Oxidation

Zhang, Longsheng; Wang, Liping; Lin, Haiping; Liu, Yunxia; Ye, Jinyu; Wen, Yunzhou; Chen, Ao; Wang, Lie; Ni, Fenglou; Zhou, Zijun; Sun, Shi‐Gang; Li, Youyong; Zhang, Bo; Peng, Huisheng

doi:10.1002/anie.201909832

Cited by 252 publications

(182 citation statements)

References 25 publications

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“…utilized high‐valence transition‐metal Ni 4+ sites that could trigger lattice oxygen at the highly active sites to couple with the *CO intermediate. [ 232 ] Notably, the Ni 4+ active sites showed ultrahigh current density and TOF values toward the UOR compared to those of the Ni 3+ active sites. The DFT calculations also revealed that the lattice‐oxygen atoms in the Ni 3+ OOH surface did not participate in the reactions, while on the NiOO surface, the lattice oxygen reacted with the *CONNH 2 intermediate to form line‐type adsorbed CO 2 molecules; this result lowers the electrocatalytic potentials and energy barriers of the potential‐independent regenerations of the active sites.…”

Section: Discussionmentioning

confidence: 99%

Designing High‐Valence Metal Sites for Electrochemical Water Splitting

Sun

Song

et al. 2021

Adv Funct Materials

252

162

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Electrochemical water splitting is a critical energy conversion process for producing clean and sustainable hydrogen; this process relies on low‐cost, highly active, and durable oxygen evolution reaction/hydrogen evolution reaction electrocatalysts. Metal cations (including transition metal and noble metal cations), particularly high‐valence metal cations that show high catalytic activity and can serve as the main active sites in electrochemical processes, have received special attention for developing advanced electrocatalysts. In this review, heterogenous electrocatalyst design strategies based on high‐valence metal sites are presented, and associated materials designed for water splitting are summarized. In the discussion, emphasis is given to high‐valence metal sites combined with the modulation of the phase/electronic/defect structure and strategies of performance improvement. Specifically, the importance of using advanced in situ and operando techniques to track the real high‐valence metal‐based active sites during the electrochemical process is highlighted. Remaining challenges and future research directions are also proposed. It is expected that this comprehensive discussion of electrocatalysts containing high‐valence metal sites can be instructive to further explore advanced electrocatalysts for water splitting and other energy‐related reactions.

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Section: Discussionmentioning

confidence: 99%

Designing High‐Valence Metal Sites for Electrochemical Water Splitting

Sun

Song

et al. 2021

Adv Funct Materials

252

162

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“…For the O 1s spectra of P-LMNO and M-LMNO samples (Figure 1 f), relative intensity of the peak at 531.66 eV increases from 12.7 % to 18.9 % after surface treatment, [14] suggesting the production of oxygen vacancies. [15] The precise level of oxygen defect is confirmed by Iodometry titration. [16] The oxygen non-stoichiometry (d) of M-LMNO sample is 0.189, which is significantly higher than that of P-LMNO .…”

mentioning

confidence: 84%

An Ultra‐Long‐Life Lithium‐Rich Li_1.2Mn_0.6Ni_0.2O₂ Cathode by Three‐in‐One Surface Modification for Lithium‐Ion Batteries

et al. 2020

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Voltage decay and capacity fading are the main challenges for the commercialization of Li‐rich Mn‐based layered oxides (LLOs). Now, a three‐in‐one surface treatment is designed via the pyrolysis of urea to improve the voltage and capacity stability of Li1.2Mn0.6Ni0.2O2 (LMNO), by which oxygen vacancies, spinel phase integration, and N‐doped carbon nanolayers are synchronously built on the surface of LMNO microspheres. Oxygen vacancies and spinel phase integration suppress irreversible O2 release and help lithium ion diffusion, while N‐doped carbon nanolayer mitigates the corrosion of electrolyte with excellent conductivity. The electrochemical performance of LMNO after the treatment improves significantly; the capacity retention rate after 500 cycles at 1 C is still as high as 89.9 % with a very small voltage fading rate of 1.09 mV cycle−1. This three‐in‐one surface treatment strategy can suppress the voltage decay and capacity fading of LLOs.

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“…The shortened RuO and IrO metal ligand bonds can increase the covalency of metal–oxygen bonds due to the lowered metal d states that are closer to oxygen 2p‐band centers (Figure S5, Supporting Information), and thus facilitate the generation of metal‐bonded electrophilic oxygen species. [ 22–25 ]…”

Section: Figurementioning

confidence: 99%

Boosting Neutral Water Oxidation through Surface Oxygen Modulation

et al. 2020

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Developing efficient electrocatalysts for oxygen evolution reaction (OER) in pH‐neutral electrolyte is crucial for microbial electrolysis cells and electrochemical CO2 reduction. Unfortunately, the OER kinetics in neutral electrolyte is sluggish due to the low concentration of adsorbed reactants, with overpotentials of neutral OER at present much higher than that in acidic or alkaline electrolyte. Here, hydrated metal cations (Ca2+) are sought to be incorporated into the state‐of‐the‐art Ru–Ir binary oxide to tailor the surface oxygen environments (lattice‐oxygen and adsorbed oxygen species) for efficient neutral OER. Using a sol–gel method, ternary Ru–Ir–Ca oxides are synthesized in atomically homogenous manner, and the obtained catalyst on glassy carbon electrode achieves 10 mA cm−2 at a low overpotential of 250 mV, with no degradation for 200 h of operation. In situ X‐ray absorption spectroscopy, in situ 18O isotope‐labeling differential electrochemical mass spectrometry, and 18O isotope‐labeling secondary ion mass spectroscopy studies are carried out. The results reveal that incorporation of Ca2+ can enhance the covalency of metal–oxygen bonds and the electrophilic nature of surface metal‐bonded oxygen sites; and simultaneously facilitate the adsorption of water molecules on catalyst surface, which accelerates the lattice‐oxygen‐involved reaction, thus improving the overall OER performance of RuIrCaOx catalyst.

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A Lattice‐Oxygen‐Involved Reaction Pathway to Boost Urea Oxidation

Cited by 252 publications

References 25 publications

Designing High‐Valence Metal Sites for Electrochemical Water Splitting

Designing High‐Valence Metal Sites for Electrochemical Water Splitting

An Ultra‐Long‐Life Lithium‐Rich Li_1.2Mn_0.6Ni_0.2O₂ Cathode by Three‐in‐One Surface Modification for Lithium‐Ion Batteries

Boosting Neutral Water Oxidation through Surface Oxygen Modulation

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A Lattice‐Oxygen‐Involved Reaction Pathway to Boost Urea Oxidation

Cited by 252 publications

References 25 publications

Designing High‐Valence Metal Sites for Electrochemical Water Splitting

Designing High‐Valence Metal Sites for Electrochemical Water Splitting

An Ultra‐Long‐Life Lithium‐Rich Li1.2Mn0.6Ni0.2O2 Cathode by Three‐in‐One Surface Modification for Lithium‐Ion Batteries

Boosting Neutral Water Oxidation through Surface Oxygen Modulation

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An Ultra‐Long‐Life Lithium‐Rich Li_1.2Mn_0.6Ni_0.2O₂ Cathode by Three‐in‐One Surface Modification for Lithium‐Ion Batteries