XPS measurement of fivefold and sixfold coordinated sulfur in pyrrhotites and evidence for millerite and pyrrhotite surface species

Nesbitt, H.W.; Schaufuß, Andrea G; Scaini, M. J.; Bancroft, G.M.; Szargan, R.

doi:10.2138/am-2001-2-315

Cited by 29 publications

(12 citation statements)

References 19 publications

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“…The S 2p spectrum of NiS 2 in Figure 3e shows two overlapping peaks around 162.5 and 163.7 eV, which correspond to the S 2p 3/2 and S 2p 1/2 signals of S 2 2− anions, respectively. [ 40,41 ] Both Ni and S signals shift to lower binding energy, indicating S vacancies leave additional electrons to v‐NiS 2 . Figure S12, Supporting Information, presents the O 1s spectrum.…”

Section: Resultsmentioning

confidence: 99%

Sulfophobic and Vacancy Design Enables Self‐Cleaning Electrodes for Efficient Desulfurization and Concurrent Hydrogen Evolution with Low Energy Consumption

Zhang

Zhou

Shen

et al. 2021

Adv Funct Materials

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Sulfide oxidation reaction (SOR) is one central step of electrochemical desulfurization and sulfur‐based batteries. However, the electrochemical performance of desulfurization and sulfur batteries has been severely hindered by sulfur passivation. Here, a discovery of sulfophobic phenomenon of electrocatalysts having weak interaction to sulfur species is reported. A self‐cleaning NiS2 electrode is developed to avoid the long‐perplexing passivation issue of solid sulfur during the SOR. Furthermore, sulfur‐vacancies are engineered into NiS2 lattice to synthesize v‐NiS2 for the hydrogen evolution reaction (HER). The resultant lattice expansion and electron redistribution can adjust the adsorbed hydrogen to reach a nearly thermos‐neutral state, enabling high catalytic activity for the HER. By coupling the HER and SOR, efficient desulfurization and simultaneous hydrogen production is demonstrated. Bifunctional NiS2 enables such a one‐stone‐kills‐two‐birds strategy to realize continuous electrochemical desulfurization with superior energy efficiency (1.05 gsulfur Wh−1). As a general design principle, sulfophobic electrocatalysts can improve the properties of lithium–sulfur batteries by minimizing the passivation of S8 during charge. In brief, interfacial interaction between electrocatalysts and sulfur species are systematically investigated and a sulfophobic strategy to significantly enhance the electrochemical performance of the SOR is offered.

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Section: Resultsmentioning

confidence: 99%

Sulfophobic and Vacancy Design Enables Self‐Cleaning Electrodes for Efficient Desulfurization and Concurrent Hydrogen Evolution with Low Energy Consumption

Zhang

Zhou

Shen

et al. 2021

Adv Funct Materials

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“…The first two contributions (at 161.5/162.7 and 162.7/163.9 eV) can be attributed to sulfide (S 2‐ ) anions occupying fivefold and sixfold sites in non‐stoichiometric Fe 7 S 8 . [ 25 ] The third doublet at 163.8/165.0 eV is assigned to S atoms in the heteroatom‐doped carbonaceous framework (CSC). The two other doublets at higher binding energy both originate from oxidized S species (166.0/167.2 eV SO x ( x < 4) and 168.2/169.4 eV SO 4 ).…”

Section: Resultsmentioning

confidence: 99%

Metal–Organic Framework Derived Fe₇S₈ Nanoparticles Embedded in Heteroatom‐Doped Carbon with Lithium and Sodium Storage Capability

Zhang

et al. 2020

Small Methods

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most common electrochemical energy storage devices, being widely used for powering portable electronics and electric vehicles, thanks to their high energy and power density. [2] In view of the limited raw materials supply, however, sodium-ion batteries (SIBs) are attracting increasing interest due to the widespread abundance of sodium (i.e., potentially lower cost), while sharing the operating principles with LIBs. [3] In this respect, SIBs are attracting special attention for large-scale energy storage devices. [4] The energy density of both LIBs and SIBs is limited by the volumetric capacity of the negative electrode (usually referred to as anode) material. This is especially true for SIBs, due to the lower specific capacity of, for example, hard carbon with respect to graphite. [5] Therefore, the development of high-performance anode materials with long cycle life and high reversible capacity is a major task for the development of next-generation LIBs and SIBs. Given the similar battery chemistries, various carbon-based materials, [6] alloy-type materials, [2a] and transition-metal oxides/ sulfides [7] have been extensively investigated for both LIBs and SIBs. Among these anode materials, transition-metal sulfides (TMSs, e.g., MnS, FeS 2 , MoS 2 , CuS, SnS 2 , and Fe 7 S 8) with a conversion reaction mechanism exhibit highly reversible capacities and intrinsic safety for lithium and sodium storage. [8] Compared to their metal oxide counterparts, TMSs usually show faster reaction kinetics owing to their higher electronic conductivity and their better mechanical integrity, resulting from the smaller volumetric change. [5a,8a] Among the various reported TMSs, iron sulfides have been recognized as one of the most promising alternative due to their cost-effectiveness, high theoretical capacity (FeS: 609 mAh g −1 , FeS 2 : 894 mAh g −1), abundance, and low toxicity. [6] Unfortunately, their practical application is still hindered by limited conversion rates and mechanical instability upon extended cycling. To address these issues, different strategies of rational structure design have been developed, including nano/microstructure engineering and decoration with conductive carbonaceous materials. For example, Shi et al. synthesized core-shell iron sulfides-carbon nanobiscuits using a hydrothermal method. [9] The as-obtained material showed high reversible capacities of 547 mAh g-1 after 600 cycles for lithium and 531 mAh g-1 after 1 000 cycles for Iron sulfides are promising materials for lithium-and sodium-ion batteries owing to their high theoretical capacity and widespread abundance. Herein, the performance of an iron sulfide-carbon composite, synthesized from a Fe-based metal-organic framework (Fe-MIL-88NH 2) is reported. The material is composed of ultrafine Fe 7 S 8 nanoparticles (<10 nm in diameter) embedded in a heteroatom (N, S, and O)-doped carbonaceous framework (Fe 7 S 8 @ HD-C), and is obtained via a simple and efficient one-step sulfidation process. The Fe 7 S 8 @HD-C composite, investigated in diethyle...

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“…This is in line with the previously observed sulfur surface state in pyrrhotite. 47 The regions at both 01 (Fig. 2a) and 701 (Fig.…”

Section: Xpsmentioning

confidence: 98%

“…The doublets at 161.4 eV and 162.5 eV are assigned to fivefold and sixfold coordinated sulfur respectively, in analogy to pyrrhotite which shares the basic NiAs structure. 30,47 The origin of the intensity encompassed by the broad doublet at higher binding energy is not clear. Intensity in this region is observed in pyrrhotite and pyrite, and has been variously assigned to polysulfide species, inadequacy of the fitted peak shape, or energy loss features, with the latter being most likely.…”

Section: Xpsmentioning

confidence: 99%

“…Intensity in this region is observed in pyrrhotite and pyrite, and has been variously assigned to polysulfide species, inadequacy of the fitted peak shape, or energy loss features, with the latter being most likely. [47][48][49][50] Table 1 Refined atomic positions for the structure of the iron sulfide film with space group 186 (P6 3 mc). hu 2 i is the isotropic mean squared thermal displacement of the atom and is related to the Debye-Waller factor by the equation B = 8p 2 hu 2 i Discounting the contribution from the surface and the additional intensity at higher binding energy, the doublet corresponding to fivefold coordinated sulfur accounts for approximately 82% of the total S 2p peak area.…”

Section: Xpsmentioning

confidence: 99%

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Growth of well-ordered iron sulfide thin films

Davis

Berti

Kuhlenbeck

et al. 2019

Phys. Chem. Chem. Phys.

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XPS measurement of fivefold and sixfold coordinated sulfur in pyrrhotites and evidence for millerite and pyrrhotite surface species

Cited by 29 publications

References 19 publications

Sulfophobic and Vacancy Design Enables Self‐Cleaning Electrodes for Efficient Desulfurization and Concurrent Hydrogen Evolution with Low Energy Consumption

Sulfophobic and Vacancy Design Enables Self‐Cleaning Electrodes for Efficient Desulfurization and Concurrent Hydrogen Evolution with Low Energy Consumption

Metal–Organic Framework Derived Fe₇S₈ Nanoparticles Embedded in Heteroatom‐Doped Carbon with Lithium and Sodium Storage Capability

Growth of well-ordered iron sulfide thin films

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XPS measurement of fivefold and sixfold coordinated sulfur in pyrrhotites and evidence for millerite and pyrrhotite surface species

Cited by 29 publications

References 19 publications

Sulfophobic and Vacancy Design Enables Self‐Cleaning Electrodes for Efficient Desulfurization and Concurrent Hydrogen Evolution with Low Energy Consumption

Sulfophobic and Vacancy Design Enables Self‐Cleaning Electrodes for Efficient Desulfurization and Concurrent Hydrogen Evolution with Low Energy Consumption

Metal–Organic Framework Derived Fe7S8 Nanoparticles Embedded in Heteroatom‐Doped Carbon with Lithium and Sodium Storage Capability

Growth of well-ordered iron sulfide thin films

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Metal–Organic Framework Derived Fe₇S₈ Nanoparticles Embedded in Heteroatom‐Doped Carbon with Lithium and Sodium Storage Capability