Electronic structure modulation of NiS<sub>2</sub> by transition metal doping for accelerating the hydrogen evolution reaction

Wang, Tongtong; Guo, Xiaosong; Zhang, Jingyan; Xiao, Wen; Xi, Pinxian; Peng, Shanglong; Gao, Daqiang

doi:10.1039/c8ta11286j

Cited by 101 publications

(53 citation statements)

References 29 publications

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“…The metal-sulfur interaction is revealed by XPS analysis, showing the emergence of the CoS/NiS bonds in the sulfur-loaded composites (Figure 2e). [37] The metal-sulfur interaction is further confirmed by the FTIR spectra, as shown in Figure 2f. In addition to the characteristic bonds vibration of metal coordinated BDC frameworks, [38] the stretching vibrations of Co-S bond (620 cm −1 ) and Ni-S bond (1053 cm −1 ) are clearly displayed in S@CoNi-MOF composites.…”

Section: Structure and Morphology Of Mof Catalystsmentioning

confidence: 65%

A Tandem Electrocatalysis of Sulfur Reduction by Bimetal 2D MOFs

Meng

Zhong

et al. 2021

Advanced Energy Materials

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polysulfide by the host materials are conventional approaches to tackle the dissolution problem, [3,4] nonetheless, these could only partially alleviate the shuttle effect due to low fraction of host material in the electrode. Using "flooded" electrolyte could dilute the polysulfide solution thus somehow improves the redox kinetics due to enhanced mass/charge transfer, although it inevitably decreases the actual energy density of the battery. [1] Alternatively, recently established proactive electrocatalysis strategy could not only effectively improve the redox kinetics but also provide a "root" solution to solve the polysulfide shuttling. [5,6] The catalyzed sulfur redox reaction showed faster conversion kinetics, especially for the conversion of soluble LiPSs into the insoluble final products, thus preventing the continuous accumulation of LiPSs in electrolyte that is responsible for the shuttle effect. [7,8] An increasing number of electrocatalysts have been applied to Li-S batteries, [5,[9][10][11][12] however, systematic study on the kinetic and underlying basis to evaluate the exact role of catalyst addressing the PS shuttling issues is still overlooked. The classic electrocatalysis process is mostly referred to as heterogeneous catalytic reaction [13] -catalyzing a specific reaction instead of a series of reactions-as exemplified by the wellestablished electrocatalysis in fuel cells and water splitting such as the oxygen reduction reaction, oxygen evolution reaction (OER), and hydrogen evolution reaction. [14,15] The electrolysis of sulfur reduction reaction is much more complicated due to the consecutive multistep reduction reaction of sulfur, which brought huge challenge for the design of catalyst. [16] The diversified intermediate products of sulfur species would dynamically disproportionate or centralize in the electrolyte solution. [17] Moreover, one specific sulfur intermediate acts as both the reactant and product for the adjacent consecutive reductions, indicating that the sulfur species in the electrocatalysis reactions are highly conjugated and coupled. In addition to the multistep conversion reactions, the sulfur conversion reaction also involves multiphase transition because the long-chain polysulfides (Li 2 S x , 4 ≤ x ≤ 8) are soluble whereas the shortchain polysulfides (Li 2 S x , 1 ≤ x ≤ 2) is insoluble in the electrolyte. [18] Only a few catalysis works have paid attention to such complicated conversion reactions but mostly focused on the The diversity and coupling of sulfur redox intermediates and its associated solid-liquid-solid multiphase conversion mechanism pose great challenges in designing a proper electrocatalysts for Li-S batteries. In this report, it is proposed that an ideal catalyst should possess two catalytic centers which catalyze liquid-liquid conversion and liquid-solid conversion in tandem within one structure, with the use of 2D MOF nanosheets with different metal centers for validation. It is uncovered that the Ni-MOF is more effective in catalyzing the reduction of lo...

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Section: Structure and Morphology Of Mof Catalystsmentioning

confidence: 65%

A Tandem Electrocatalysis of Sulfur Reduction by Bimetal 2D MOFs

Meng

Zhong

et al. 2021

Advanced Energy Materials

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“…The calculated electronic density of states (DOS) in Figure 1c shows the semiconducting nature of NiS 2 with a bandgap of ≈2.4 eV, which is in good agreement with previously reported values. [ 12 ] After replacing a Ni atom by a Cu atom, the DOS of Cu‐NiS 2 demonstrates the metallic‐like behavior, which is beneficial for electron transfer during electrocatalysis (Figure 1c). This transition is attributed to the contribution from d orbitals of Cu atoms.…”

Section: Resultsmentioning

confidence: 99%

Electronic Modulation of Nickel Disulfide toward Efficient Water Electrolysis

Dinh

Sun

Pei

et al. 2020

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friendly and sustainable sources of power are being looked at in order to meet the demand. Among all the developing technologies, solar-light-coupled electrochemical water splitting is widely perceived as one of the best solutions due to the generation of hydrogen -a sustainable and clean source of energy. [1] It is known that noble group compounds, namely Pt and RuO 2 /IrO 2 , are the state-of-the-art electrocatalysts toward two critical half-reactions of water splitting -hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). [2] However, the high price and natural shortage impede their further application. Therefore, developing lowcost, efficient electrocatalyst is urgently desired.Motivated by the challenge, a wide range of materials have been investigated and developed. [3] Among them, nickelbased materials have attracted a great deal of attention mainly because their eight valence electrons in 3d orbitals enable the easy alteration of electronic structure through phase engineering (laser-induced, mechanical strain, weak Ar plasma treatment, e-beam irradiation, and plasmonic hotelectron-induced), heterostructuring (NiS 2 -MoS 2 , Ni 3 S 2 -MoS 2 , V-Ni 2 P). [3c,4] A representative compound in this nickel-based family, pyrite-type nickel sulfides (NiS 2 ) is emerging as a highly Developing highly efficient earth-abundant nickel-based compounds is an important step to realize hydrogen generation from water. Herein, the electronic modulation of the semiconducting NiS 2 by cation doping for advanced water electrolysis is reported. Both theoretical calculations and temperaturedependent resistivity measurements indicate the semiconductor-to-conductor transition of NiS 2 after Cu incorporation. Further calculations also suggest the advantages of Cu dopant to cathodic water electrolysis by bringing Gibbs free energy of H adsorption at both Ni sites and S sites much closer to zero. It is noteworthy that water dissociation on Cu-doped NiS 2 (Cu-NiS 2 ) surface is even more favorable than those on NiS 2 and Pt(111). Thus, the prepared Cu-NiS 2 shows noticeably improved performance toward alkaline hydrogen and oxygen evolution reactions (HER and OER). Specifically, it requires merely 232 mV OER overpotential to drive 10 mA cm −2 ; in parallel with Tafel slopes of 46 mV dec −1 . Regarding HER, an onset overpotential of only 68 mV is achieved. When integrated as both electrodes for water electrolysis, Cu-NiS 2 needs only 1.64 V to drive 10 mA cm −2 , surpassing the state-of-the-art Ir/C-Pt/C couple (1.71 V). This work opens up an avenue to engineer low-cost and earth-abundant catalysts performing on par with the noble-metal-based one for water splitting.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.

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“…The results indicated that the functional from GGA-PBE provides the best agreement with the experimental data [26][27], which have a relative deviation of 1.02% as compared to other functions. As for the Fe-doped NiS 2 , it shows that the Fe doping does not alter the lattice constant that much due to the atomic radius of Fe and Ni is quite close [28]. The average bond length of the atoms in NiS 2 and Fe-doped NiS 2 was calculated by using GGA-PBE, which are presented in Table 2.…”

Section: Structural Propertiesmentioning

confidence: 94%

First-Principles Studies on Structural, Electronic and Optical Properties of Fe-doped Nis2 Counter Electrode for Dye-Sensitized Solar Cells using Dft+U

et al. 2020

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The structural, electronic and optical properties of nickel disulfide (NiS2) and iron (Fe)-doped NiS2 were computed by using first-principles calculations through the density functional theory (DFT) method. The Fe was used as a dopant element to understand the behavior and the key mechanism of Fe-doped NiS2 as a counter electrode in dye-sensitized solar cells (DSSC). The results indicated that the structural properties of the NiS2 as the cubic crystal structure with the space group Pa3 (205) (pyrite structure type) agree with experimental data. The density of states (DOS) of NiS2 and Fe-doped NiS2 shows a gapless bandgap due to Mott insulator behavior. As for optical properties, the optical absorption of NiS2 is shifted towards the infrared (IR) region when doping with Fe while the conductivity of Fe-doped NiS2 is slightly higher in conductivity. These optical properties show that Fe-doped NiS2 is good for photocatalytic activity and may provide an excellent electron charge transfer for a counter electrode in DSSC

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Electronic structure modulation of NiS₂ by transition metal doping for accelerating the hydrogen evolution reaction

Abstract: We give a systematic study of the HER catalytic activity of transition metal doped NiS2 by first principles calculations and experiments.

Cited by 101 publications

References 29 publications

A Tandem Electrocatalysis of Sulfur Reduction by Bimetal 2D MOFs

A Tandem Electrocatalysis of Sulfur Reduction by Bimetal 2D MOFs

Electronic Modulation of Nickel Disulfide toward Efficient Water Electrolysis

First-Principles Studies on Structural, Electronic and Optical Properties of Fe-doped Nis2 Counter Electrode for Dye-Sensitized Solar Cells using Dft+U

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Electronic structure modulation of NiS2 by transition metal doping for accelerating the hydrogen evolution reaction

Abstract: We give a systematic study of the HER catalytic activity of transition metal doped NiS2 by first principles calculations and experiments.

Cited by 101 publications

References 29 publications

A Tandem Electrocatalysis of Sulfur Reduction by Bimetal 2D MOFs

A Tandem Electrocatalysis of Sulfur Reduction by Bimetal 2D MOFs

Electronic Modulation of Nickel Disulfide toward Efficient Water Electrolysis

First-Principles Studies on Structural, Electronic and Optical Properties of Fe-doped Nis2 Counter Electrode for Dye-Sensitized Solar Cells using Dft+U

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Electronic structure modulation of NiS₂ by transition metal doping for accelerating the hydrogen evolution reaction