Unveiling the Promotion of Surface‐Adsorbed Chalcogenate on the Electrocatalytic Oxygen Evolution Reaction

Shi, Yanmei; Du, Wei; Zhou, Wei; Wang, Changhong; Lu, Sen; Lu, Siyu; Zhang, Bin

doi:10.1002/anie.202011097

Cited by 309 publications

(263 citation statements)

References 48 publications

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“…The overall and the high-resolution Se 3d spectra of NiPS and Ni 2p 1/2 with a binding energy of 854.96 and 872.32 eV, respectively, as well as two satellite peaks. [31,32] Clearly, the incorporation of Se into NiPS 3 NSs causes a gradual shift of the Ni 2p peaks to lower binding energies, which suggests that Ni cations are reduced to a lower valence state. The high-resolution S 2p spectra of NiPS 3-x Se x NSs (Figure 2e) show two peaks at 164.09 and 162.93 eV, corresponding to the S 2p 1/2 and S 2p 3/2 , [22,33] which also display a similar shift.…”

Section: Resultsmentioning

confidence: 99%

Sub‐2 nm Thiophosphate Nanosheets with Heteroatom Doping for Enhanced Oxygen Electrocatalysis

Song

Qiu

et al. 2021

Adv Funct Materials

146

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Developing an efficient bifunctional electrocatalyst with accelerated kinetics is important but challenging for rechargeable metal‐air batteries. In this study, a series of anion‐regulated sub‐2 nm ultrathin thiophosphate nanosheets (NiPS3–xSex NSs) is rationally designed and synthesized as bifunctional oxygen evolution/reduction reaction (OER/ORR) electrocatalysts for Zn‐air batteries. The increase of nominal Se dopants (0 ≤ x ≤ 0.5) leads to the expansion of (001) crystal plane spacing and partially disordered structure generation after the incorporation of Se to pristine NiPS3. More importantly, electronic structures of active sites can be reasonably regulated via coordination of the interaction between anions and cations. Density functional theory calculations reveal that such tailored electronic structures reduce the overpotential of the thermodynamic barriers step for both OER and ORR as well as shorten energy bandgap, which can accelerate reaction kinetics in electrocatalytic processes and enhance electrical conductivity. Consequently, the obtained NiPS3–xSex NSs exhibit low OER overpotential (250 mV) and positive ORR onset potential (0.94 V), large power density (152 mW cm−2), and robust stability (96 h cycle) for Zn‐air devices, far exceeding that of precious metal catalysts. This study provides a novel tactic to design earth‐abundant and highly efficient bifunctional electrocatalysts for metal‐air battery technologies.

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Section: Resultsmentioning

confidence: 99%

Sub‐2 nm Thiophosphate Nanosheets with Heteroatom Doping for Enhanced Oxygen Electrocatalysis

Song

Qiu

et al. 2021

Adv Funct Materials

146

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“…Thus, the structural transformation of metal and metal alloys is often neglected. Besides, some ions in the electrolyte are proven to influence the electrode reaction activity, [12] such as Fe 3+ on OER, [13] and NO 3 À on the nitrogen reduction. [14] However, the effects of the ions, especially the ones generated from cathode materials themselves, are rarely explored for the electroreduction process.…”

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confidence: 99%

Unveiling the In Situ Dissolution and Polymerization of Mo in Ni₄Mo Alloy for Promoting the Hydrogen Evolution Reaction

et al. 2021

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NiMo alloys are efficient electrocatalysts in alkaline water electrolyzer for the hydrogen evolution reaction (HER). Metals are usually considered to be stable during the cathodic process. However, the actual behaviors of Mo in the NiMo alloys are unexplored. Here, we present the instability of Mo in the Ni 4 Mo alloy as a highly efficient HER electrocatalyst in an alkaline medium. Mo in Ni 4 Mo is oxidized and dissolved in the form of MoO 4 2À first. The dissolved MoO 4 2À will re-adsorb on the electrode surface and polymerize. Theoretical calculations indicate that the adsorption of the dimer Mo 2 O 7 2À can promote the HER activity of metal Ni. The addition of MoO 4 2À to the electrolyte can not only repair the durability of Ni 4 Mo alloy, but also facilitate the HER activity of pure metal of Ni, Fe, and Co. Our findings provide insight into the structural transformation mechanism and performance-enhanced origin of cathodic materials under the reaction conditions.

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“…To insight into how CLs promote reaction kinetics, OH activation/dissociation that strongly determine fast kinetics were investigated via in situ Raman, FT-IR spectroscope, pH-dependent and deuterium kinetic isotope effects (KIEs). It is well known that Lewis bases (SO 4 2− /PO 4 3− /COO − /CO 3 2− /SeO 4 2− ) in solution are a proton acceptor, 41 which can be utilized as a transfer station for protons to facilitate the proton transmission rate, evenly perform the functions of OH activation and dissociation. To verify above hypothesis and explain why NiFeMn-MOF possesses a remarkably superior reaction kinetics, in situ Raman measurement was rstly carried out.…”

Section: Resultsmentioning

confidence: 99%

Surface‐Adsorbed Carboxylate Ligands on Layered Double Hydroxides/Metal–Organic Frameworks Promote the Electrocatalytic Oxygen Evolution Reaction

Zhao

Xie

et al. 2021

Angewandte Chemie

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Metal-organic frameworks (MOFs) with carboxylate ligands as co-catalysts are very e cient for oxygen evolution reaction (OER). However, the role of local adsorbed carboxylate ligands around the in situ transformed metal (oxy)hydroxides during OER is often overlooked. Here we reveal the extraordinary role and mechanism of surface adsorbed carboxylate ligands on bi/trimetallic layered double hydroxides (LDHs)/MOFs for OER catalytic activity enhancement. The results of X-ray photoelectron spectroscopy (XPS), synchrotron X-ray absorption spectroscopy and theoretical calculations show that the carboxylic groups around metal (oxy)hydroxides can e ciently induce the interfacial electron redistribution, facilitate abundant high-valence state of nickel species with partial distorted octahedral structure, and optimize the d-band center together with the bene cial Gibbs free energy of intermediate. Furthermore, the results of in-situ Raman and FI-IR spectra rstly reveal that the surface adsorbed carboxylate ligands as Lewis base can promote the sluggish OER kinetics by accelerating proton transfer and facilitating adsorption/ activation/dissociation of hydroxyl ions (OH − ). Our ndings will offer unique insights into the reason for disclosing the origin of excellent electrocatalytic activity for MOF/NiFe-LDHs catalysts.

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Unveiling the Promotion of Surface‐Adsorbed Chalcogenate on the Electrocatalytic Oxygen Evolution Reaction

Cited by 309 publications

References 48 publications

Sub‐2 nm Thiophosphate Nanosheets with Heteroatom Doping for Enhanced Oxygen Electrocatalysis

Sub‐2 nm Thiophosphate Nanosheets with Heteroatom Doping for Enhanced Oxygen Electrocatalysis

Unveiling the In Situ Dissolution and Polymerization of Mo in Ni₄Mo Alloy for Promoting the Hydrogen Evolution Reaction

Surface‐Adsorbed Carboxylate Ligands on Layered Double Hydroxides/Metal–Organic Frameworks Promote the Electrocatalytic Oxygen Evolution Reaction

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Unveiling the Promotion of Surface‐Adsorbed Chalcogenate on the Electrocatalytic Oxygen Evolution Reaction

Cited by 309 publications

References 48 publications

Sub‐2 nm Thiophosphate Nanosheets with Heteroatom Doping for Enhanced Oxygen Electrocatalysis

Sub‐2 nm Thiophosphate Nanosheets with Heteroatom Doping for Enhanced Oxygen Electrocatalysis

Unveiling the In Situ Dissolution and Polymerization of Mo in Ni4Mo Alloy for Promoting the Hydrogen Evolution Reaction

Surface‐Adsorbed Carboxylate Ligands on Layered Double Hydroxides/Metal–Organic Frameworks Promote the Electrocatalytic Oxygen Evolution Reaction

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Unveiling the In Situ Dissolution and Polymerization of Mo in Ni₄Mo Alloy for Promoting the Hydrogen Evolution Reaction